Polycarbonate-poly(alkylene oxide) copolymer compositions and articles formed therefrom

ABSTRACT

Disclosed herein is a polycarbonate copolymer comprising A) a structure derived from a dihydroxy alkylene oxide compound selected from the group consisting of formula (1a) and formula (1b): 
       H-(E-X) l —OH   (1a) 
       H-(E-X-E) l -OH   (1b)         wherein E and X are different and each and independently are selected from the group consisting of formula (2a) and formula (2b):       
       —(OCH 2 CH 2 ) m —   (2a) 
       —(OCHRCH 2 ) n —   (2b)         wherein R is a C 1-8  alkyl group; l, m, and n are integers greater than or equal to 1; and wherein the weight average molecular weight of the total amount of the structures corresponding to formula (2b) in the copolymer is between 100 and 2,000 g/mol; and B) a structure derived from a dihydroxy aromatic compound, wherein the weight percentages are based on the total weight of the structures of A) and B).

BACKGROUND OF THE INVENTION

This disclosure relates to polycarbonates, and in particular topolycarbonate-poly(alkylene oxide) copolymers, blends withpolycarbonates, and uses thereof.

Polycarbonates are useful in the manufacture of articles and componentsfor a wide range of applications including medical devices.Polycarbonates having excellent attributes including an inherently(i.e., permanently) hydrophilic surface are particularly desirable forsuch devices. A permanently hydrophilic polycarbonate surface isimportant for applications where the ability of water to wet a surfaceis critical. Such applications include filters and membranes where ahydrophilic surface is needed to prevent air bubbles and to improve flowthrough a membrane.

It is known in the art that copolycarbonates can be made withpoly(ethylene oxide) (also referred to herein as “poly(ethyleneglycol)”) blocks to improve surface wettability. At least in partbecause of their good hemocompatibility properties, such polycarbonatesare useful in medical packaging applications. However, polycarbonateswith PEG blocks can have low glass transition temperatures and aretherefore less able to withstand high temperature and high pressuresterilization (autoclave) conditions without deformation compared topolycarbonates having none or a lower amount of units derived fromethylene oxide. Conversely, increased levels of carbonate units based onbisphenols such as bisphenol A that would provide the requisite thermaldeformation resistance generally have higher surface contact angle andcan result in reduced hemocompatibility. However, increased levels ofthe ethylene oxide units can also lead to increased haze in thecompositions.

There accordingly remains a need in the art for polycarbonates that haveimproved surface wettability, together with other advantageousproperties, such as thermal stability, hemocompatibility, anti-fogging,and improved transparency.

SUMMARY OF THE INVENTION

The above-described and other deficiencies of the art are met by athermoplastic composition comprising a polycarbonate copolymercomprising A) 5 to 30 weight percent of a structure derived from adihydroxy alkylene oxide compound selected from the group consisting offormula (1a) and formula (1b):

H-(E-X)_(l)—OH  (1a)

H-(E-X-E)_(l)-OH  (1b)

wherein E and X are different and each and independently are selectedfrom the group consisting of formula (2a) and formula (2b):

—(OCH₂CH₂)_(m)—  (2a)

—(OCHRCH₂)_(n)—  (2b)

wherein R is a C₁₋₈ alkyl group; l, m, and n are integers greater thanor equal to 1; and wherein the weight average molecular weight of thetotal amount of the structures corresponding to formula (2b) in thecopolymer is between 100 and 2,000 g/mol; and B) 70 to 95 weight percentof a structure derived from a dihydroxy aromatic compound, wherein theweight percentages are based on the total weight of the structures of A)and B).

In another embodiment, a polycarbonate copolymer comprises A) 5 to 30weight percent of a structure derived from a dihydroxy alkylene oxidecompound selected from the group consisting of formula (1a) and formula(1b):

H-(E-X)_(l)—OH  (1a)

H-(E-X-E)_(l)-OH  (1b)

wherein E and X are different and each and independently are selectedfrom the group consisting of formula (2a) and formula (2b):

—(OCH₂CH₂)_(m)—  (2a)

—(OCHRCH₂)_(n)—  (2b)

wherein R is a C₁₋₈ alkyl group; l, m, and n are integers greater thanor equal to 1; and wherein the weight average molecular weight of thetotal amount of the structures corresponding to formula (2b) in thecopolymer is between 100 and 2,000 g/mol; and B) 70 to 95 weight percentof a structure derived from a dihydroxy aromatic compound, wherein theweight percentages are based on the total weight of the structures of A)and B), and wherein the polycarbonate comprises structural units derivedfrom an activated aromatic carbonate.

In another embodiment, a method of preparing a polycarbonate copolymercomprises copolymerizing: A) 5 to 30 weight percent of a dihydroxyalkylene oxide compound selected from the group consisting of formula(1a) and formula (1b):

H-(E-X)_(l)—OH  (1a)

H-(E-X-E)_(l)-OH  (1b)

wherein E and X are different and each and independently are selectedfrom the group consisting of formula (2a) and formula (2b):

—(OCH₂CH₂)_(m)—  (2a)

—(OCHRCH₂)_(n)—  (2b)

wherein R is a C₁₋₈ alkyl group; l, m, and n are integers greater thanor equal to 1; and wherein the weight average molecular weight of thetotal amount of the structures corresponding to formula (2b) in thecopolymer is between 100 and 2,000 g/mol; and B) 70 to 95 weight percentof a dihydroxy aromatic compound, wherein the weight percentages arebased on the total weight of the structures of A) and B); with acarbonylating agent.

In another embodiment, a method comprises reacting together, in thepresence of a catalyst: A) 5 to 30 weight percent of a dihydroxyalkylene oxide compound selected from the group consisting of formula(1a) and formula (1b):

H-(E-X)_(l)—OH  (1a)

H-(E-X-E)_(l)-OH  (1b)

wherein E and X are different and each and independently are selectedfrom the group consisting of formula (2a) and formula (2b):

—(OCH₂CH₂)_(m)—  (2a)

—(OCHRCH₂)_(n)—  (2b)

wherein R is a C₁₋₈ alkyl group; l, m, and n are integers greater thanor equal to 1; and wherein the weight average molecular weight of thetotal amount of the structures corresponding to formula (2b) in thecopolymer is between 100 and 2,000 g/mol; and B) 70 to 95 weight percentof a dihydroxy aromatic compound, wherein the weight percentages arebased on the total weight of the structures of A) and B); and one ormore activated diaryl carbonate of the formula (12):

wherein Ar is a substituted C₆₋₃₀ aromatic group.

In another embodiment, a polycarbonate copolymer comprises: A) astructural unit derived from a dihydroxy alkylene oxide compoundselected from the group consisting of formula (1a) and formula (1b):

H-(E-X)_(l)—OH  (1a)

H-(E-X-E)_(l)-OH  (1b)

wherein E and X are different and each and independently are selectedfrom the group consisting of formula (2a) and formula (2b):

—(OCH₂CH₂)_(m)—  (2a)

—(OCHRCH₂)_(n)—  (2b)

wherein R is a C₁-C₈ alkyl group; l, m, and n are integers greater thanor equal to 1; and B) a structural unit derived from a high-heat monomercomprising a dihydroxy aromatic compound of formula (7):

wherein R^(a′) and R^(b′) are each independently C₁₋₁₂ alkyl, T is aC₅₋₁₆ cylcloalkylidene or C₆₋₁₆ heterocycloarylene having up to threeheteroatoms in the ring, wherein T is connected to at least one atom ofeach aromatic ring in the dihydroxy aromatic compound, wherein theheteroatoms include —O—, —S—, or —N(Z)-, and Z is hydrogen, halogen,hydroxy, C₁₋₁₂ alkyl, C₁₋₁₂ alkoxy, C₆₋₁₂ aryl, or C₁₋₁₂ acyl, andwherein r and s are each independently 0 to 4.

In an embodiment, a polycarbonate copolymer, comprises: A) a structuralunit derived from a dihydroxy alkylene oxide compound selected from thegroup consisting of formula (1a) and formula (1b):

H-(E-X)_(l)—OH  (1a)

H-(E-X-E)_(l)-OH  (1b)

wherein E and X are different and each and independently are selectedfrom the group consisting of formula (2a) and formula (2b):

—(OCH₂CH₂)_(m)—  (2a)

—(OCHRCH₂)_(n)—  (2b)

wherein R is a C₁-C₈ alkyl group; l, m, and n are integers greater thanor equal to 1; and B) a structural unit derived from a high-heat monomercomprising a dihydroxy aromatic compound of formula (7):

wherein R^(a′) and R^(b′) are each independently C₁₋₁₂ alkyl, T is aC₅₋₁₆ cylcloalkylidene or C₆₋₁₆ heterocycloarylene having up to threeheteroatoms in the ring, wherein T is connected to at least one atom ofeach aromatic ring in the dihydroxy aromatic compound, wherein theheteroatoms include —O—, —S—, or —N(Z)-, and Z is hydrogen, halogen,hydroxy, C₁₋₁₂ alkyl C₁₋₁₂ alkoxy, C₆₋₁₂ aryl, or C₁₋₁₂ acyl, wherein rand s are each independently 0 to 4, and wherein the polycarbonatecomprises structural units derived from an activated aromatic carbonate.

In an embodiment, a method of preparing a polycarbonate copolymercomprises copolymerizing: A) a dihydroxy alkylene oxide compoundselected from the group consisting of formula (1a) and formula (1b):

H-(E-X)_(l)—OH  (1a)

H-(E-X-E)_(l)-OH  (1b)

wherein E and X are different and each independently are selected fromthe group consisting of formula (2a) and formula (2b):

—(OCH₂CH₂)_(m)—  (2a)

—(OCHRCH₂)_(n)—  (2b)

wherein R is a C₁-C₈ alkyl group; l, m, and n are integers greater thanor equal to 1; and B) a high heat monomer comprising a dihydroxyaromatic compound of formula (7):

wherein R^(a′) and R^(b′) are each independently C₁₋₂ alkyl, T is aC₅₋₁₆ cylcloalkylidene or C₅₋₁₆ heterocycloarylene having up to threeheteroatoms in the ring, wherein T is connected to at least one atom ofeach aromatic ring in the dihydroxy aromatic compound, wherein theheteroatoms include —O—, —S—, or —N(Z)-, and Z is hydrogen, halogen,hydroxy, C₁₋₁₂ alkyl, C₁₋₁₂ alkoxy, C₆₋₁₂ aryl, or C₁₋₁₂ acyl, andwherein r and s are each independently 0 to 4; and a carbonylatingagent.

In another embodiment, a method comprises reacting together, in thepresence of a catalyst: A) a dihydroxy alkylene oxide compound selectedfrom the group consisting of formula (1a) and formula (1b):

H-(E-X)_(l)—OH  (1a)

H-(E-X-E)_(l)-OH  (1b)

wherein E and X are different and each independently are selected fromthe group consisting of formula (2a) and formula (2b):

—(OCH₂CH₂)_(m)—  (2a)

—(OCHRCH₂)_(n)—  (2b)

wherein R is a C₁-C₈ alkyl group; l, m, and n are integers greater thanor equal to 1; B) a high heat monomer comprising a dihydroxy aromaticcompound of formula (7):

wherein R^(a′) and R^(b′) are each independently C₁₋₁₂ alkyl, T is aC₅₋₁₆ cylcloalkylidene or C₅₋₁₆ heterocycloarylene having up to threeheteroatoms in the ring, wherein T is connected to at least one atom ofeach aromatic ring in the dihydroxy aromatic compound, wherein theheteroatoms include —O—, —S—, or —N(Z)-, and Z is hydrogen, halogen,hydroxy, C₁₋₁₂ alkyl, C₁₋₁₂ alkoxy, C₆₋₁₂ aryl, or C₁₋₁₂ acyl, andwherein r and a are each independently 0 to 4; and one or more activateddiaryl carbonate of the formula (12):

wherein Ar is a substituted C₆₋₃₀ aromatic group.

In another embodiment, an article comprises the polycarbonatecompositions.

A description of the figures, which are meant to be exemplary and notlimiting, is provided below.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a plot of contact angle versus loading of PEG-PPG forexemplary PEG/PPG polycarbonate copolymers;

FIG. 2 is a plot of haze versus Mw of PPG for exemplary PEG/PPGpolycarbonate copolymers;

FIG. 3 is a plot of percent transmittance (% T) versus Mw of PPG forexemplary PEG/PPG polycarbonate copolymers;

The above described and other features are exemplified by the followingdetailed description.

DETAILED DESCRIPTION OF THE INVENTION

Described herein is a polycarbonate copolymer (also referred to as a“copolycarbonate”) derived from: a dihydroxy aromatic compound; and adihydroxy alkylene oxide compound, specifically a dihydroxypoly(alkylene oxide) block copolymer. In one embodiment, the dihydroxyaromatic compound can comprise a bisphenol, and the dihydroxypoly(alkylene oxide) block copolymer comprises at least onepoly(ethylene oxide) block and at least one poly(alkylene oxide) blockthat is not identical to the poly(ethylene oxide) block. In anotherembodiment, the dihydroxy aromatic compound comprises a high heatmonomer. The polycarbonate copolymers, and thermoplastic compositionsprepared therefrom, have improved surface contact angle as well as otheradvantageous properties, such as improved hemocompatibility,wettability, and haze and/or transparency. The copolycarbonates areparticularly useful in medical applications.

Polycarbonates, as used herein, include polymers having carbonatelinkages. In particular, polycarbonates including the copolycarbonatesdescribed herein have repeating carbonate structural units of theformula (3):

wherein the R¹ groups are derived from dihydroxy aromatic compounds asdescribed in detail below.

The polycarbonate copolymer generally comprises structural units whereat least a portion of the R¹ groups derive from dihydroxy aromaticcompounds having a bisphenol structure. In one embodiment, the dihydroxyaromatic compound comprises units derived from a bisphenol of theformula (4):

wherein R^(a) and R^(b) each independently represent a halogen or C₁₋₁₂alkyl; p and q are each independently integers of 0 to 4. It will beunderstood that when p and/or q is 0, the valency will be filled by ahydrogen atom. Also in formula (4), X^(a) represents a bridging groupconnecting the two hydroxy-substituted aromatic groups (i.e.,hydroxy-substituted C₆ arylene groups such as, for example, phenol oro-cresol), where the bridging group and the hydroxy substituent of theC₆ arylene group are disposed para to each other on the C₆ arylenegroup. In an embodiment, the bridging group X^(a) is a C₁₋₁₈ organicgroup. The C₁₋₁₈ organic bridging group can be cyclic or acyclic,aromatic or non-aromatic, and can further comprise heteroatoms such ashalogens, oxygen, nitrogen, sulfur, silicon, or phosphorous. The C₁₋₁₈organic group can be disposed such that the C₆ arylene groups connectedthereto are each connected to a common alkylidene carbon or to differentcarbons of the C₁₋₁₈ organic bridging group.

In an embodiment, X^(a) is —O—, —S—, —S(O)—, —S(O)₂—, or one of thegroups of formula (5):

wherein R^(c) and R^(d) are each independently hydrogen, C₁₋₁₂ alkyl,cyclic C₁₋₁₂ alkyl, C₇₋₁₂ arylalkyl, C₁₋₁₂ heteroalkyl, or cyclic C₇₋₁₂heteroarylalkyl, and R^(e) is a divalent C₁₋₁₂ hydrocarbon group.

In another embodiment, X^(a) is a C₁₋₁₈ alkylene group, a C₃₋₁₈cycloalkylene group, a fused C₆₋₁₈ cycloalkylene group, or a group ofthe formula —B¹—W—B²— wherein B¹ and B² are the same or different C₁₋₆alkylene group and W is a C₃₋₁₂ cycloalkylene group or a C₆₋₁₆ arylenegroup.

In still another embodiment, X^(a) is an acyclic C₁₋₁₈ alkylidene group,a C₃₋₁₈ cycloalkylidene group (except for a cyclohexylidene), or a C₂₋₁₈heterocycloalkylidene group, i.e., a cycloalkylidene group having up tothree heteroatoms in the ring, wherein the heteroatoms include —O—, —S—,or —N(Z)-, where Z is hydrogen, halogen, hydroxy, C₁₋₁₂ alkyl, C₁₋₁₂alkoxy, or C₁₋₁₂ acyl.

X^(a) can be a substituted C₃₋₁₈ cycloalkylidene of the formula (6):

wherein each R^(r), R^(p), R^(q), and R^(t) is independently hydrogen,halogen, oxygen or C₁₋₁₂ organic group; I is a direct bond, a carbon, ora divalent oxygen, sulfur, or —N(Z)- wherein Z is hydrogen, halogen,hydroxy, C₁₋₁₂ alkyl, C₁₋₁₂ alkoxy, or C₁₋₁₂ acyl; h is 0 to 2, j is 0to 2, i is 0 or 1, and k is 0 to 3, with the proviso that at least twoof R^(r), R^(p), R^(q) and R^(t) taken together are a fusedcycloaliphatic, aromatic, or heteroaromatic ring. It will be understoodthat where the fused ring is aromatic, the ring as shown in formula (6)will have an unsaturated carbon-carbon linkage where the ring is fused.When k is 1 and i is 0, the ring as shown in formula (6) contains 4carbon atoms, when k is 2, the ring as shown contains 5 carbon atoms,and when k is 3, the ring contains 6 carbon atoms. In one embodiment,two adjacent groups (e.g., R^(q) and R^(t) taken together) form anaromatic group, and in another embodiment, R^(q) and R^(t) takentogether form one aromatic group and R^(r) an R^(p) taken together forma second aromatic group.

In a specific embodiment, a bisphenol that differs from the bisphenol offormula (4) and is copolymerized therewith to provide thecopolycarbonate is derived from a dihydroxy aromatic compound having theformula (4a):

wherein R^(a) and R^(b) are each independently halogen or C₁₋₁₂ alkyl;R^(c) and R^(d) are each independently hydrogen, C₁₋₁₂ alkyl, cyclicC₁₋₁₂ alkyl, C₇₋₁₂ arylalkyl, C₁₋₁₂ heteroalkyl, or cyclic C₇₋₁₂heteroarylalkyl; and p and q are each independently 0 to 4.

Some illustrative, non-limiting examples of suitable bisphenol compoundsinclude the following: 4,4′-dihydroxybiphenyl, 1,6-dihydroxynaphthalene,2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane,bis(4-hydroxyphenyl)diphenylmethane,bis(4-hydroxyphenyl)-1-naphthylmethane, 1,2-bis(4-hydroxyphenyl)ethane,1,1-bis(4-hydroxyphenyl)-1-phenylethane,2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane,bis(4-hydroxyphenyl)phenylmethane,2,2-bis(4-hydroxy-3-bromophenyl)propane,1,1-bis(hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxy-3 methylphenyl)cyclohexane1,1-bis(4-hydroxyphenyl)isobutene,1,1-bis(4-hydroxyphenyl)cyclododecane,trans-2,3-bis(4-hydroxyphenyl)-2-butene,2,2-bis(4-hydroxyphenyl)adamantine,(alpha,alpha′-bis(4-hydroxyphenyl)toluene,bis(4-hydroxyphenyl)acetonitrile,2,2-bis-(3-methyl-4-hydroxyphenyl)propane,2,2-bis(3-ethyl-4-hydroxyphenyl)propane,2,2-bis(3-n-propyl-4-hydroxyphenyl)propane,2,2-bis(3-isopropyl-4-hydroxyphenyl)propane,2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane,2,2-bis(3-t-butyl-4-hydroxyphenyl)propane,2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,2,2-bis(3-allyl-4-hydroxyphenyl)propane,2,2-bis(3-methoxy-4-hydroxyphenyl)propane,2,2-bis(4-hydroxyphenyl)hexafluoropropane,1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dibromo-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dichloro-2,2-bis(5-phenoxy-4-hydroxyphenyl)ethylene,4,4′-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone,1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, ethylene glycolbis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether,bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide,bis(4-hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorene,2,7-dihydroxypyrene, and 9,9-bis(4-hydroxyphenyl)fluorene,3,3-bis(4-hydroxyphenyl)phthalide, 2,6-dihydroxydibenzo-p-dioxin,2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxathin,2,7-dihydroxy-9,10-dimethylphenazine, 3,6-dihydroxydibenzofuran,3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole, and the like,as well as combinations comprising at least one of the foregoingdihydroxy aromatic compounds.

Specific examples of the types of bisphenol compounds represented byformula (4) include 1,1-bis(4-hydroxyphenyl)methane,1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane(hereinafter “bisphenol A” or “BPA”), 2,2-bis(4-hydroxyphenyl)butane,2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)propane,1,1-bis(4-hydroxyphenyl)n-butane,2,2-bis(4-hydroxy-1-methylphenyl)propane,1,1-bis(4-hydroxy-t-butylphenyl)propane. Combinations comprising atleast one of the foregoing dihydroxy aromatic compounds can also beused.

In a more specific embodiment, a bisphenol monomer of formula (3)comprises, but is not limited to, a dihydroxy aromatic compound of theformula (7):

wherein R^(a′) and R^(b′) are each independently C₁₋₁₂ alkyl, T is aC₅₋₁₆ cycloalkylene, a C₅₋₁₆ cylcloalkylidene, a C₁₋₅ alkylene, a C₁₋₅alkylidene, a C₆₋₁₃ arylene, a C₇₋₁₂ arylalkylene, C₇₋₁₂ arylalkylidene,a C₇₋₁₂ alkylarylene, or a C₇₋₁₂ arylenealkyl, and r and s are eachindependently 1 to 4. T is connected to at least one atom of eacharomatic ring in the dihydroxy aromatic compound. Each of the foregoinggroups are unsubstituted or substituted with an alkyl, aryl, alkoxy, oraryloxy group (up to the indicated total number of carbon atoms),halogen, —CN, —NO₂, —SH, or —OH. Combinations of the substituents can bepresent.

In a specific embodiment, T is a C₅₋₁₆ cylcloalkylidene or C₅₋₁₆heterocycloarylene of general formula (6) having up to three heteroatomsin the ring. The heteroatoms include —O—, —S—, or —N(Z)-, where Z ishydrogen, halogen, hydroxy, C₁₋₁₂ alkyl, C₁₋₁₂ alkoxy, C₆₋₁₂ aryl, orC₁₋₁₂ acyl, and wherein r and s are each independently 0 to 4. T can beunsubstituted or substituted with one or more of alkyl, aryl, alkoxy, oraryloxy group (up to the indicated total number of carbon atoms),halogen, —CN, —NO₂, —SH, or —OH. In addition, T is connected to at leastone atom of each aromatic ring in the dihydroxy aromatic compound, andcan therefore have a single point of attachment to each phenolic ring ofthe bisphenol, or can form a fused and/or polycyclic ring system withthe bisphenols.

Specifically, the units of formula (3) can be derived from a monomercomprising a C₆ cycloalkylidene-bridged bisphenol of formula (8):

wherein R^(a′) and R^(b′) are each independently C₁₋₁₂ alkyl, R^(g) isC₁₋₁₂ alkyl or halogen, r and s are each independently 0 to 4, and t is0 to 10. It will be understood that hydrogen fills each valency when ris 0, s is 0, and t is 0. In a specific embodiment, where r and/or s is1 or greater, at least one of each of R^(a′) and R^(b′) are disposedmeta to the cyclohexylidene bridging group. The substituents R^(a′),R^(b′), and R^(g) may, when comprising an appropriate number of carbonatoms, be straight chain, cyclic, bicyclic, branched, saturated, orunsaturated. In a specific embodiment, R^(a′), R^(b′), and R^(g) areeach C₁₋₄ alkyl, specifically methyl. In still another embodiment,R^(a′), R^(b′), and R^(g) is a C₁₋₃ alkyl, specifically methyl, r and sare 0 or 1, and t is 0 to 5, specifically 0 to 3.

In a specific embodiment, the cyclohexylidene bridged bisphenol offormula (8) can be a 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane(“DMBPC”), having the formula (8a):

In a further embodiment, at least a portion of the R¹ groups of formula(3) are derived from a high heat monomer. A high heat monomer is adihydroxy compound which, when polymerized into a polycarbonatehomopolymer, imparts a higher glass transition temperature than would beobtained with a polycarbonate homopolymer derived from bisphenol Amonomer. High heat monomers can be derived from dihydroxy aromaticcompounds of formulas (7) or (8). For example, in a specific embodiment,a high heat monomer can be a cycloalkylidene-bridged bisphenol offormula (8), comprising the reaction product of two moles of phenol withone mole of a hydrogenated isophorone (e.g.,1,1,3-trimethyl-1-cyclohexane-5-one). Such a high heat monomer can havethe formula (8b):

wherein the monomer of formula (8b) is marketed under the tradename“APEC®” by Bayer Corporation and is referred to generally as “bisphenolisophorone” (“BPI”).

In another specific embodiment, as a high heat monomer, thecycloalkylidene-bridged bisphenol is a cyclopentadienyl-bridgedbisphenol derived from the reaction of 5-cyclopentadienone with twomoles of phenol, as shown in the formula (8c), and referred to as“tricyclopentadienyl bisphenol” (“TCDBP”):

In another embodiment, the high heat monomer can comprise aspiro-bridged, fused ring dihydroxyaromatic compound of the formula (9):

wherein R^(a″), R^(b″), and R^(k) are independently C₁₋₁₂ hydrocarbyl,each x is independently an integer from 0 to 4, and y and z are eachindependently an integer from 0 to 3. In a more specific embodiment, thedihydroxyaromatic compound has the formula (9a):

wherein R^(a″), R^(b″) are independently C₁₋₄ alkyl, C₁₋₄ alkoxy, and yand z are each independently 0 or 1. In an exemplary embodiment, where wand z are 0, the high heat monomer is6,6′-dihydroxy-3,3,3′,3′-tetramethylspiro(bis)indane (“spirobiindanebisphenol”).

In another specific embodiment, T in the high heat monomer of formula(7) is a substituted, fused C₅₋₁₈ heterocycloalkylidene of the formula(6), forming a fused heteroaromatic ring. In a specific embodiment, thehigh heat monomer has the formula (10):

wherein R^(i), R^(j), and R^(k) are independently C₁₋₁₂ hydrocarbyl, Gis H, a C₁₋₁₂ alkyl, or C₆₋₁₈ aromatic group, and u, v, and w are eachindependently an integer from 0 to 4. In an exemplary embodiment, thehigh heat monomer is 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine(“PPPBP”), having the formula (10a):

In other embodiments, exemplary high heat monomers that are usefulherewith include at least one selected from3,3-bis(4-hydroxyphenyl)phthalimidine phenolphthalein (PPN),1,1-bis(4-hydroxyphenyl)fluorenone (BCF);2,2-bis(4-hydroxyphenyl)adamantane; and1,1-bis(4-hydroxyphenyl)-1-phenyl ethane (BPAP). It will be understoodthat the foregoing high heat monomers are included as exemplaryembodiments, and that the high heat monomers useful herein should not beconsidered as limited thereto.

Small amounts of other types of diols can be present in thecopolycarbonate. For example, a small portion of R¹ can be derived froma dihydroxy aromatic compound of formula (11):

wherein each R^(f) is independently C₁₋₁₂ alkyl, or halogen, and u is 0to 4. It will be understood that R^(f) is hydrogen when u is 0.Typically, the halogen can be chlorine or bromine. In an embodiment,compounds of formula (11) in which the —OH groups are substituted metato one another, and wherein R^(f) and u are as described above, are alsogenerally referred to herein as resorcinols. Examples of compounds thatcan be represented by the formula (11) include resorcinol (where u is0), substituted resorcinol compounds such as 5-methyl resorcinol,5-ethyl resorcinol, 5-propyl resorcinol, 5-butyl resorcinol, 5-t-butylresorcinol, 5-phenyl resorcinol, 5-cumyl resorcinol, 2,4,5,6-tetrafluororesorcinol, 2,4,5,6-tetrabromo resorcinol, or the like; catechol;hydroquinone; substituted hydroquinones such as 2-methyl hydroquinone,2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone,2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone,2,3,5,6-tetramethyl hydroquinone, 2,3,5,6-tetra-t-butyl hydroquinone,2,3,5,6-tetrafluoro hydroquinone, 2,3,5,6-tetrabromo hydroquinone, orthe like; or combinations comprising at least one of the foregoingcompounds.

The copolycarbonate further comprises a structural unit derived from adihydroxy alkylene oxide compound. Specifically, the dihydroxy alkyleneoxide compound is a dihydroxy end-capped poly(alkylene oxide) blockcopolymer comprising at least two structurally different blocks, eachhaving different surface activity properties. In particular, the desiredfeature for the dihydroxy end-capped poly(alkylene oxide) blockcopolymer is that it possess a first block which has highhydrophilicity, and a second block having lower hydrophilicity, relativeto the first block. Suitable poly(alkylene oxide) block copolymershaving this feature and which are useful herein comprise structuralunits selected from the group consisting of formula (1a) and formula(1b):

H-(E-X)_(l)—OH  (1a)

H-(E-X-E)_(l)-OH  (1b)

wherein E and X are different and each and independently are selectedfrom the group consisting of formula (2a) and formula (2b):

—(OCH₂CH₂)_(m)—  (2a)

—(OCHRCH₂)_(n)—  (2b)

wherein R is a C₁-C₈ alkyl group, and l, m, and n are integers greaterthan or equal to 1. In an embodiment, m is 2 to 120; n is 2 to 50; and 1is 1 to 3. It will be understood that, where a range of numbers is usedthat corresponds to the values of m and n, an average value for each ofthese is intended. In a specific embodiment, the polycarbonate copolymercomprises a dihydroxy alkylene oxide compound of either or both offormulas (1a) or (1b) in which l is 1; i.e., a diblock copolymer is usedwhere l is 1 for formula (1a), and a triblock copolymer where l is 1 forformula (1b). In a specific embodiment, R is methyl.

In an embodiment, for either or both of formulas (1a) or (1b), Ecorresponds to formula (2a), and X corresponds to formula (2b). Also inan embodiment, m is 2 to 55, specifically 2 to 50, and more specifically2 to 40; and n is 2 to 50, specifically 3 to 35, and more specifically 3to 20.

In another embodiment, for either or both of formulas (1a) or (1b), Xcorresponds to formula (2a), and E corresponds to formula (2b). Also inan embodiment, m is 3 to 120, specifically 4 to 100, and morespecifically 5 to 80; and n is 2 to 30, specifically 2 to 25, and morespecifically 2 to 20.

In an embodiment, the weight averaged molecular weight (Mw) of the totalamount of the structures corresponding to formula (2b) in the copolymeris between 100 and 2,000 g/mol, specifically 200 to 1,500 g/mol, andstill more specifically 300 to 1,200 g/mol.

In a specific embodiment, the dihydroxy alkylene oxide compound is a di-or triblock copolymer having ethylene oxide (i.e., 1,2-ethylene oxide)repeating units, also referred to herein as ethylene glycol units, in afirst block, and propylene oxide (i.e., 1,2-propylene oxide) repeatingunits, also referred to herein as propylene glycol units, in a secondblock. As used herein, a block comprising ethylene oxide units isreferred to as a poly(ethylene oxide) block, and may also be referred toas a poly(ethylene glycol) block. Similarly, as used herein, a blockcomprising propylene oxide units is referred to as a poly(propyleneoxide) block, and may also be referred to as a poly(propylene glycol)block. Specifically, in an embodiment, a first block consistsessentially of ethylene oxide units, and a second block consistsessentially of propylene oxide units. It is contemplated that the firstblock and/or the second block can itself be a homo- or copolymercomprising either or both of ethylene oxide groups of formula (2a) andpropylene oxide groups of formula (2b) (where R is methyl), so long asthe desired surface activity properties of the dihydroxy alkylene oxidecopolymer, and the polycarbonate copolymer derived therefrom, ismaintained. In an exemplary embodiment, useful dihydroxy alkylene oxidecompounds include the PLURONIC® (a trademark of BASF Corporation) seriesof compounds which are block copolymers available from BASF Corporationand having the general block structures PEG-PPG, PEG-PPG-PEG, andPPG-PEG-PPG (the R series) where PEG is poly(ethylene glycol) and PPG ispoly(propylene glycol).

Any proportion by weight of the dihydroxy alkylene oxide compound anddihydroxy aromatic compound is contemplated, provided that the desiredproperties of the resulting polycarbonate copolymer is maintained. In anembodiment, the dihydroxy alkylene oxide compound is present in anamount of 5 to 30 weight percent (wt %), specifically 5 to 20 wt %, morespecifically 7 to 15 wt %, based on the total weight of structural unitsderived from dihydroxy alkylene oxide compound and dihydroxy aromaticcompound. Also in an embodiment, structural units derived from thedihydroxy aromatic compound are present in the polycarbonate copolymerin an amount of 70 to 95 wt %, specifically 80 to 95 wt %, and morespecifically 85 to 93 wt %, based on the total weight of structuralunits derived from dihydroxy alkylene oxide compound and dihydroxyaromatic compound. In another embodiment, the dihydroxy aromaticcompound comprises a combination of two or more, non-identical dihydroxyaromatic compounds.

In an embodiment, the polycarbonate copolymer comprises structural unitsderived from a dihydroxy alkylene oxide compound of formulas (1a) or(1b), and at least one dihydroxy aromatic compound of formula (4). In anembodiment, where there are two or more dihydroxy aromatic compounds,the two or more dihydroxy aromatic compounds are all of general formula(4). In another embodiment, the polycarbonate copolymer consistsessentially of structural units derived from the dihydroxy alkyleneoxide compound, and structural units derived from the dihydroxy aromaticcompound. In an embodiment, the polycarbonate copolymer consistsessentially of the foregoing proportions of structural units derivedfrom the dihydroxy alkylene oxide compound and dihydroxy aromaticcompound where the dihydroxy aromatic compound is a compound of formula(4). Where the polycarbonate copolymer comprises structural unitsderived from formula (4) (and does not include structural units derivedfrom formula (7)), the Mw of the formula (2b) in the copolymer isbetween 100 and 2,000 g/mol. In an exemplary embodiment, thepolycarbonate copolymer consists of structural units derived from anethylene oxide-propylene oxide di- or triblock copolymer and structuralunits derived from bisphenol A.

In another embodiment, the polycarbonate copolymer comprises structuralunits derived from a dihydroxy alkylene oxide compound of formulas (1a)or (1b), and at least one dihydroxy aromatic compound of formula (7). Inan embodiment, where two or more dihydroxy aromatic compounds are used,at least one is of formula (7) and the other is of formula (4). Inanother embodiment, the polycarbonate copolymer consists essentially ofstructural units derived from the dihydroxy alkylene oxide compound, andstructural units derived from the dihydroxy aromatic compound. In anexemplary embodiment, the polycarbonate copolymer consists of structuralunits derived from an ethylene oxide-propylene oxide di- or triblockcopolymer and structural units derived from PPPBP.

In an embodiment, where the polycarbonate copolymer comprises structuralunits derived from a high heat monomer of formula (7), the structuralunits derived from the dihydroxy alkylene oxide compound are present inan amount of 0.1 to 30 wt %, specifically 0.5 to 25 wt %, and morespecifically 1 to 20 wt % based on the total weight of structural unitsderived from dihydroxy alkylene oxide compound, high heat monomer, andany additional dihydroxy aromatic compound not identical to the highheat monomer used.

In an embodiment, the weight average molecular weight of thepolycarbonate copolymer is 5,000 to 100,000 g/mol, specifically 7,500 to75,000 g/mol, and still more specifically 10,000 to 50,000 g/mol,measured using gel permeation chromatography (GPC) on a crosslinkedstyrene-divinylbenzene column as calibrated to polycarbonate references.GPC samples are prepared in a solvent such as methylene chloride orchloroform at a concentration of about 1 mg/ml, and are eluted at a flowrate of about 0.5-1.5 ml/min.

The polycarbonate copolymer can be substantially transparent. In thiscase, an article (e.g., a plaque) having a thickness of 3.2 mm andmolded from the polycarbonate copolymer can have a haze of less than orequal to about 5%, specifically less than or equal to about 3%, and morespecifically less than or equal to about 2%, according to ASTM-D1003-00.Similarly, an article having a thickness of 3.2 mm and molded from thepolycarbonate copolymer can have a percent transmittance (% T) ofgreater than or equal to about 70%, specifically greater than or equalto about 80%, and more specifically greater than or equal to about 90%,according to ASTM-D1003-00.

The polycarbonate copolymers can be manufactured using an interfacialphase transfer process or melt polymerization as is known. Although thereaction conditions for interfacial polymerization can vary, anexemplary process generally involves dissolving or dispersing a dihydricphenol reactant in aqueous caustic soda or potash, adding the resultingmixture to a water-immiscible solvent medium, and contacting thereactants with a carbonate precursor in the presence of a catalyst suchas, for example, triethylamine or a phase transfer catalyst salt, undercontrolled pH conditions, e.g. about 8 to about 10. Suitable phasetransfer catalysts include compounds of the formula (R³)₄Q⁺X, whereineach R³ is the same or different, and is a C₁₋₁₀ alkyl group; Q is anitrogen or phosphorus atom; and X is a halogen atom or a C₁₋₈ alkoxygroup or C₆₋₁₈ aryloxy group. Exemplary phase transfer catalyst saltsinclude, for example, [CH₃(CH₂)₃]₄NX, [CH₃(CH₂)₃]₄PX, [CH₃(CH₂)₅]₄NX,[CH₃(CH₂)₆]₄NX, [CH₃(CH₂)₄]₄NX, CH₃[CH₃(CH₂)₃]₃NX, andCH₃[CH₃(CH₂)₂]₃NX, wherein X is Cl⁻, Br⁻, a C₁₋₈ alkoxy group or a C₆₋₁₈aryloxy group.

Exemplary carbonate precursors include, for example, a carbonyl halidesuch a carbonyl bromide or carbonyl chloride, or a haloformate such as abishaloformates of a dihydric phenol (e.g., the bischloroformates ofbisphenol A, hydroquinone, or the like) or a glycol (e.g., thebishaloformate of ethylene glycol, neopentyl glycol, polyethyleneglycol, or the like). Combinations comprising at least one of theforegoing types of carbonate precursors can also be used. In oneembodiment, the process uses phosgene as a carbonate precursor.

The water-immiscible solvent used to provide a biphasic solutionincludes, for example, methylene chloride, 1,2-dichloroethane,chlorobenzene, toluene, and the like.

Alternatively, melt processes can be used to make the polycarbonatecopolymer. Generally, in the melt polymerization process, polycarbonatesmay be prepared by co-reacting, in a molten state, the dihydroxyreactant(s) and a diaryl carbonate ester, such as diphenyl carbonate, inthe presence of a transesterification catalyst. The reaction may becarried out in typical polymerization equipment, such as one or morecontinuously stirred reactors (CSTR's), plug flow reactors, wire wettingfall polymerizers, free fall polymerizers, wiped film polymerizers,Banbury® mixers, single or twin screw extruders, or combinations of theforegoing. Volatile monohydric phenol is removed from the moltenreactants by distillation and the polymer is isolated as a moltenresidue. A specifically useful melt process for making polycarbonatesuses a diaryl carbonate ester having electron-withdrawing substituentson the aryls. Examples of specifically useful diaryl carbonate esterswith electron withdrawing substituents includebis(4-nitrophenyl)carbonate, bis(2-chlorophenyl)carbonate,bis(4-chlorophenyl)carbonate, bis(methyl salicyl)carbonate,bis(4-methylcarboxylphenyl)carbonate, bis(2-acetylphenyl)carboxylate,bis(4-acetylphenyl)carboxylate, or a combination comprising at least oneof the foregoing. In addition, exemplary transesterification catalystsmay include phase transfer catalysts of formula (R³)₄Q⁺X above, whereineach R³, Q, and X are as defined above Examples of suchtransesterification catalysts include tetrabutylammonium hydroxide,methyltributylammonium hydroxide, tetrabutylammonium acetate,tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate,tetrabutylphosphonium phenolate, or a combination comprising at leastone of the foregoing. Other melt transesterification catalysts includealkaline earth metal salts or alkali metal salts.

In an embodiment, where a melt process is used, a thermal stabilizer canbe added to the polymerization to mitigate or eliminate any potentialdegradation of the dihydroxy alkylene oxide compound during the hightemperatures (up to about 350° C. or higher) of the melt polymerization.It is known that poly(propylene glycol) polymers are susceptible tothermal degradation, and therefore inclusion of a thermal stabilizer canreduce the degree of decomposition of the dihydroxy alkylene oxidecompound and thereby provide a lower level of impurity and lead tohigher batch-to-batch consistency in the desired properties of thepolycarbonate composition.

The use of a melt process employing an activated carbonate isparticularly preferred. As used herein, the term “activated carbonate”,also at times referred to as activated diarylcarbonate, is defined as adiarylcarbonate that is more reactive than diphenylcarbonate intransesterification reactions. In an embodiment, the activated carbonatehas a formula (12):

wherein Ar is a substituted C₆₋₃₀ aromatic group. In a specificembodiment, the activated carbonates have the formula (13):

wherein Q¹ and Q² are each independently an activating group present onA¹ and A² respectively, positioned ortho to the carbonate linkage; A¹and A² are each independently aromatic rings which can be the same ordifferent; “d” and “e” have a value of 0 to a maximum equivalent to thenumber of replaceable hydrogen groups substituted on the aromatic ringsA¹ and A² respectively, and the sum “d+e” is greater than or equal to 1;R¹ and R² are each independently a C₁₋₃₀ aliphatic group, a C₃₋₃₀cycloaliphatic group, a C_(5,-30) aromatic group, cyano, nitro orhalogen; “b” has a value of 0 to a maximum equivalent to the number ofreplaceable hydrogen atoms on the aromatic ring A¹ minus “d”; and “c” isa whole number from 0 to a maximum equivalent to the number ofreplaceable hydrogen atoms on the aromatic ring A² minus “e”. Thenumber, type and location of the R¹ or R² substituents on the aromaticring is not limited unless they deactivate the carbonate and lead to acarbonate, which is less reactive than diphenylcarbonate.

Non-limiting examples of suitable activating groups Q¹ and Q² include(alkoxycarbonyl)aryl groups, halogens, nitro groups, amide groups,sulfone groups, sulfoxide groups, or imine groups with structures shownbelow:

wherein X is halogen or nitro; M¹ and M² independently compriseN-dialkyl, N-alkylaryl, an aliphatic functionality or an aromaticfunctionality; and R³ is an aliphatic functionality or an aromaticfunctionality.

Specific non-limiting examples of activated carbonates includebis(o-methoxycarbonylphenyl)carbonate, bis(o-chlorophenyl)carbonate,bis(o-nitrophenyl)carbonate, bis(o-acetylphenyl)carbonate,bis(o-phenylketonephenyl)carbonate, bis(o-formylphenyl)carbonate.Unsymmetrical combinations of these structures where the type and numberof substitutions on A¹ and A² are different can also be used as thecarbonate precursor. In an embodiment, the activated carbonate is anester-substituted diarylcarbonate having the formula (14):

wherein R⁴ is independently at each occurrence a C₁₋₂₀ aliphatic group,a C₄₋₂₀ cycloaliphatic group, or a C₄₋₂₀ aromatic group, R⁵ isindependently at each occurrence a halogen atom, cyano group, nitrogroup, a C₁₋₂₀ aliphatic group, a C₄₋₂₀ cycloaliphatic group, or a C₄₋₂₀aromatic group and f is independently at each occurrence an integerhaving a value of 0 to 4. In one embodiment, at least one of thesubstituents —CO₂R⁴ is attached in an ortho position of formula (14).

Examples of specific ester-substituted diarylcarbonates include, but arenot limited to, bis(methylsalicyl)carbonate (CAS Registry No.82091-12-1) (also known as BMSC orbis(o-methoxycarbonylphenyl)carbonate), bis(ethylsalicyl)carbonate,bis(propylsalicyl)carbonate, bis(butylsalicyl)carbonate,bis(benzylsalicyl)carbonate, bis(methyl-4-chlorosalicyl)carbonate andthe like. In one embodiment, bis(methylsalicyl)carbonate is used as theactivated carbonate in melt polycarbonate synthesis due to its lowermolecular weight and higher vapor pressure.

Some non-limiting examples of non-activating groups which, when presentin an ortho position, would not be expected to result in activatedcarbonates are alkyl, cycloalkyl or cyano groups. Some specific andnon-limiting examples of non-activated carbonates arebis(o-methylphenyl)carbonate, bis(p-cumylphenyl)carbonate,bis(p-(1,1,3,3-tetramethyl)butylphenyl)carbonate andbis(o-cyanophenyl)carbonate. Unsymmetrical combinations of thesestructures may also be used as non-activated carbonates.

An end-capping agent (also referred to as a chain-stopper) can be usedto limit molecular weight growth rate, and so control molecular weightin the polycarbonate. Exemplary chain-stoppers include certainmonophenolic compounds (i.e., phenyl compounds having a single freehydroxy group), monocarboxylic acid chlorides, and/ormonochloroformates. Phenolic chain-stoppers are exemplified by phenoland C₁-C₂₂ alkyl-substituted phenols such as p-cumyl-phenol, resorcinolmonobenzoate, and p- and tertiary-butyl phenol, cresol, and monoethersof diphenols, such as p-methoxyphenol. Alkyl-substituted phenols withbranched chain alkyl substituents having 8 to 9 carbon atoms can bespecifically mentioned. Certain monophenolic UV absorbers can also beused as a capping agent, for example4-substituted-2-hydroxybenzophenones and their derivatives, arylsalicylates, monoesters of diphenols such as resorcinol monobenzoate,2-(2-hydroxyaryl)-benzotriazoles and their derivatives,2-(2-hydroxyaryl)-1,3,5-triazines and their derivatives, and the like.Endgroups can derive from the carbonyl source as well as any addedend-capping groups. Thus, in an embodiment, a polycarbonate can comprisea structural unit derived from the carbonyl source. In a furtherembodiment, the carbonyl source is derived from an activated ornon-activated carbonate. In a specific embodiment, where BMSC is used asthe carbonyl source, the endgroup is derived from BMSC.

Suitable monocarboxylic acid chlorides include monocyclic,mono-carboxylic acid chlorides such as benzoyl chloride, C₁-C₂₂alkyl-substituted benzoyl chloride, toluoyl chloride,halogen-substituted benzoyl chloride, bromobenzoyl chloride, cinnamoylchloride, 4-nadimidobenzoyl chloride, and combinations thereof;polycyclic, mono-carboxylic acid chlorides such as trimellitic anhydridechloride, and naphthoyl chloride; and combinations of monocyclic andpolycyclic mono-carboxylic acid chlorides. Chlorides of aliphaticmonocarboxylic acids with less than or equal to about 22 carbon atomsare useful. Functionalized chlorides of aliphatic monocarboxylic acids,such as acryloyl chloride and methacryoyl chloride, are also useful.Also useful are monochloroformates including monocyclicmonochloroformates, such as phenyl chloroformate, C₁-C₂₂alkyl-substituted phenyl chloroformate, p-cumyl phenyl chloroformate,toluene chloroformate, and combinations thereof.

Various types of polycarbonates with branching groups are contemplatedas being useful, provided that such branching does not significantlyadversely affect desired properties of the compositions. Branchedpolycarbonate blocks can be prepared by adding a branching agent duringpolymerization. These branching agents include polyfunctional organiccompounds containing at least three functional groups selected fromhydroxyl, carboxyl, carboxylic anhydride, haloformyl, and mixtures ofthe foregoing functional groups. Specific examples include trimelliticacid, trimellitic anhydride, trimellitic trichloride, tris-p-hydroxyphenyl ethane, isatin-bis-phenol, tris-phenol TC(1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA(4(4(1,1-bis(p-hydroxyphenyl)-ethyl)alpha,alpha-dimethyl benzyl)phenol),4-chloroformyl phthalic anhydride, trimesic acid, and benzophenonetetracarboxylic acid. The branching agents can be added at a level ofabout 0.05 to about 2.0 wt %. Mixtures comprising linear polycarbonatesand branched polycarbonates can be used.

For certain applications, a permanently hydrophilic polycarbonatesurface is important where the ability of water to wet a surface iscritical. Such applications include, for example, filters and membraneswhere a hydrophilic surface is needed to prevent air bubbles and toimprove flow through a membrane. Copolycarbonates having poly(ethyleneglycol) blocks, which have a high hydrophilicity relative tohomopolycarbonates, are known to increase the hydrophilicity of apolycarbonate. Increasing amounts of PEG can lead to increasedhydrophilicity, as measured by water contact angle. However, inclusionof PEG blocks within polycarbonates, which have relatively highmiscibility, has been found to adversely affect other desired propertiesof the polycarbonate when the PEG is present in amounts effective toprovide a hydrophilic surface, such as the glass transition temperature(Tg) of the resulting PEG-polycarbonate copolymer, which can besignificantly reduced in glass transition temperature relative to anunmodified polycarbonate of the same composition but without PEG. Thedecrease in Tg can lead to undesired shape distortion of articlesprepared using such copolymers during high heat operations (such asautoclaving to sterilize the article).

The hydrophilicity of a surface can be measured by the contact angle ofa sessile drop of contaminant-free water placed on the surface, andmeasuring the tangential angle of contact between the drop and thesurface. For polycarbonate, the contact angle is typically about 80° orgreater indicating a relatively low wettability for a polymericsubstrate. For a surface of an article made from polycarbonate, surfaceswith greater hydrophilicity (i.e., lower contact angle) have improvedwettability.

Surprisingly, it has been found that polycarbonate copolymers containinga surface-active block (e.g., poly(propylene glycol), PPG) immediatelyadjacent to the poly(ethylene glycol) (PEG) block, have increasedhydrophilicity at lower loadings of the PEG. While not wishing to bebound by theory, it is believed the surface-active block helps conveythe poly(ethylene glycol) to the surface, thereby also increasing thesurface availability of the hydrophilic PEG block. The advantage of thistype of construction is that poly(ethylene glycol) tends to be misciblewith polycarbonate and is not surface-active; however, with thesurface-active block next to the poly(ethylene glycol) block, theresulting surface has a lower contact angle indicating increasedhydrophilicity at the surface.

These copolymers can have other advantageous properties as well, such asimproved transparency, and improved compatibility (wettability) withbiological fluids, particularly blood and blood products (i.e.,hemocompatibility). For hydrophilic surfaces, there is less retention(by adhesion) of blood components that are passed over a hydrophilicsurface, particularly, there is less retention by adhesion of cells suchas platelets, proteins, and other such components relative to the amountretained at the surface of a homopolycarbonate such as bisphenol Apolycarbonate. In an exemplary embodiment, lower platelet adhesionindicates an improvement in hemocompatibility. Thus, an article moldedfrom the polycarbonate composition has a % platelet adhesion that islower than that of a comparative article molded from a typicalpolycarbonate, such as for example bisphenol A polycarbonate.

Additionally, copolymers and terpolymers using high heat monomers (suchas PPPBP) are also provided. It has been found that introduction of anamount of a high heat monomer into a PEG-PPG/bisphenol A copolymer caneffectively increase the glass transition temperature of the resultingterpolymer, and may in this way be used as a compositional adjustment totarget a specific surface hydrophilicity. In an exemplary embodiment ofa terpolymer, a BPA/PPPBP/PLURONIC® terpolymer can be made with a glasstransition temperature comparable to that of the Tg of bisphenol Apolycarbonate homopolymer.

In an embodiment, the surface contact angle of an article molded fromthe polycarbonate copolymer is less than or equal to 70°, specificallyless than or equal to 68°, and more specifically less than or equal to65°, where the surface contact angle is measured using a sessile waterdrop measurement technique.

In an embodiment, an article molded from the polycarbonate copolymer hasa % platelet adhesion of less than 19%, specifically less than or equalto 15%, and still more specifically less than or equal to 10%, of thatof a comparable article molded from bisphenol A polycarbonate.

The polycarbonate copolymer can be combined with other components toprovide a thermoplastic composition, where types and amounts of theother components are present such that the desired properties of thethermoplastic composition are not significantly adversely affected bythese other components. In an embodiment, the thermoplastic compositionconsists essentially of the polycarbonate composition.

Any additives, including additional polymers, are contemplated providedthey do not significantly adversely affect the desired properties of thepolycarbonate copolymer. In this way, combinations of the polycarbonatecopolymer with other thermoplastic polymers are contemplated, forexample combinations with homopolycarbonates, other polycarbonatecopolymers comprising different R¹ moieties in the carbonate units,polyester carbonates, also known as polyester-polycarbonates, andpolyesters, polysiloxane-polycarbonates, or combination of these,provided the additional polymer is not identical to the polycarbonatecopolymer disclosed herein. When used, the additional polymer can bepresent in the thermoplastic composition in an amount of 1 to 30 wt %,specifically 1 to 20 wt %, more specifically 2 to 15 wt %, based on thetotal weight of polycarbonate copolymer, and the additional polymer. Inan embodiment, the thermoplastic composition consists essentially of thepolycarbonate, and any additional polymer. In an exemplary embodiment,an additional polymer can be a linear homopolycarbonate polymer derivedfrom bisphenol A.

In addition to the polycarbonate copolymer and any additional polymer,the thermoplastic composition can further comprise additives, providedthat any additives included in the thermoplastic composition do notsignificantly adversely affect the desired properties of thethermoplastic composition.

For example, the thermoplastic composition can further include impactmodifier(s). Suitable impact modifiers are typically high molecularweight elastomeric materials derived from olefins, monovinyl aromaticmonomers, acrylic and methacrylic acids and their ester derivatives, aswell as conjugated dienes. The polymers formed from conjugated dienescan be fully or partially hydrogenated. The elastomeric materials can bein the form of homopolymers or copolymers, including random, block,radial block, graft, and core-shell copolymers. Combinations of impactmodifiers can be used.

A specific type of impact modifier is an elastomer-modified graftcopolymer comprising (i) an elastomeric (i.e., rubbery) polymersubstrate having a Tg less than about 10° C., more specifically lessthan about −10° C., or more specifically about −40° C. to −80° C., and(ii) a rigid polymeric superstrate grafted to the elastomeric polymersubstrate. Materials suitable for use as the elastomeric phase include,for example, conjugated diene rubbers, for example polybutadiene andpolyisoprene; copolymers of a conjugated diene with less than about 50wt % of a copolymerizable monomer, for example a monovinylic compoundsuch as styrene, acrylonitrile, n-butyl acrylate, or ethyl acrylate;olefin rubbers such as ethylene propylene copolymers (EPR) orethylene-propylene-diene monomer rubbers (EPDM); ethylene-vinyl acetaterubbers; silicone rubbers; elastomeric C₁₋₈ alkyl(meth)acrylates;elastomeric copolymers of C₁₋₈ alkyl(meth)acrylates with butadieneand/or styrene; or combinations comprising at least one of the foregoingelastomers. Materials suitable for use as the rigid phase include, forexample, monovinyl aromatic monomers such as styrene and alpha-methylstyrene, and monovinylic monomers such as acrylonitrile, acrylic acid,methacrylic acid, and the C₁-C₆ esters of acrylic acid and methacrylicacid, specifically methyl methacrylate.

Specific exemplary elastomer-modified graft copolymers include thoseformed from styrene-butadiene-styrene (SBS), styrene-butadiene rubber(SBR), styrene-ethylene-butadiene-styrene (SEBS), ABS(acrylonitrile-butadiene-styrene),acrylonitrile-ethylene-propylene-diene-styrene (AES),styrene-isoprene-styrene (SIS), methyl methacrylate-butadiene-styrene(MBS), and styrene-acrylonitrile (SAN).

Impact modifiers are generally present in amounts of 1 to 30 parts byweight, based on 100 parts by weight of polycarbonate copolymer and anyadditional polymer.

Possible fillers or reinforcing agents include, for example, silicatesand silica powders such as aluminum silicate (mullite), syntheticcalcium silicate, zirconium silicate, fused silica, crystalline silicagraphite, natural silica sand, or the like; boron powders such asboron-nitride powder, boron-silicate powders, or the like; oxides suchas TiO₂, aluminum oxide, magnesium oxide, or the like; calcium sulfate(as its anhydride, dihydrate or trihydrate); calcium carbonates such aschalk, limestone, marble, synthetic precipitated calcium carbonates, orthe like; talc, including fibrous, modular, needle shaped, lamellartalc, or the like; wollastonite; surface-treated wollastonite; glassspheres such as hollow and solid glass spheres, silicate spheres,cenospheres, aluminosilicate (armospheres), or the like; kaolin,including hard kaolin, soft kaolin, calcined kaolin, kaolin comprisingvarious coatings known in the art to facilitate compatibility with thepolymeric matrix resin, or the like; single crystal fibers or “whiskers”such as silicon carbide, alumina, boron carbide, iron, nickel, copper,or the like; fibers (including continuous and chopped fibers) such asasbestos, carbon fibers, glass fibers, such as E, A, C, ECR, R, S, D, orNE glasses, or the like; sulfides such as molybdenum sulfide, zincsulfide or the like; barium compounds such as barium titanate, bariumferrite, barium sulfate, heavy spar, or the like; metals and metaloxides such as particulate or fibrous aluminum, bronze, zinc, copper andnickel or the like; flaked fillers such as glass flakes, flaked siliconcarbide, aluminum diboride, aluminum flakes, steel flakes or the like;fibrous fillers, for example short inorganic fibers such as thosederived from blends comprising at least one of aluminum silicates,aluminum oxides, magnesium oxides, and calcium sulfate hemihydrate orthe like; natural fillers and reinforcements such as wood flour obtainedby pulverizing wood, fibrous products such as cellulose, cotton, sisal,jute, starch, cork flour, lignin, ground nut shells, corn, rice grainhusks or the like; organic fillers such as polytetrafluoroethylene;reinforcing organic fibrous fillers formed from organic polymers capableof forming fibers such as poly(ether ketone), polyimide,polybenzoxazole, poly(phenylene sulfide), polyesters, polyethylene,aromatic polyamides, aromatic polyimides, polyetherimides,polytetrafluoroethylene, acrylic resins, poly(vinyl alcohol) or thelike; as well as additional fillers and reinforcing agents such as mica,clay, feldspar, flue dust, fillite, quartz, quartzite, perlite, tripoli,diatomaceous earth, carbon black, or the like, or combinationscomprising at least one of the foregoing fillers or reinforcing agents.

The fillers and reinforcing agents can be coated with a layer ofmetallic material to facilitate conductivity, or surface treated withsilanes to improve adhesion and dispersion with the polymeric matrixresin. In addition, the reinforcing fillers can be provided in the formof monofilament or multifilament fibers and can be used individually orin combination with other types of fiber, through, for example,co-weaving or core/sheath, side-by-side, orange-type or matrix andfibril constructions, or by other methods known to one skilled in theart of fiber manufacture. Exemplary co-woven structures include, forexample, glass fiber-carbon fiber, carbon fiber-aromatic polyimide(aramid) fiber, and aromatic polyimide fiberglass fiber or the like.Fibrous fillers can be supplied in the form of, for example, rovings,woven fibrous reinforcements, such as 0-90 degree fabrics or the like;non-woven fibrous reinforcements such as continuous strand mat, choppedstrand mat, tissues, papers and felts or the like; or three-dimensionalreinforcements such as braids. Fillers are generally used in amounts ofabout 1 to about 20 parts by weight, as on 100 parts by weight ofpolycarbonate copolymer and any additional polymer.

Exemplary antioxidant additives include, for example, organophosphitessuch as tris(nonyl phenyl)phosphite,tris(2,4-di-t-butylphenyl)phosphite,bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite or the like; alkylated monophenols orpolyphenols; alkylated reaction products of polyphenols with dienes,such astetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane,or the like; butylated reaction products of para-cresol ordicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenylethers; alkylidene-bisphenols; benzyl compounds; esters ofbeta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydricor polyhydric alcohols; esters ofbeta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid withmonohydric or polyhydric alcohols; esters of thioalkyl or thioarylcompounds such as distearylthiopropionate, dilaurylthiopropionate,ditridecylthiodipropionate,octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionateor the like; amides ofbeta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid or the like, orcombinations comprising at least one of the foregoing antioxidants.Antioxidants are generally used in amounts of about 0.01 to about 0.1parts by weight, based on 100 parts by weight of polycarbonate copolymerand any additional polymer.

Exemplary heat stabilizer additives include, for example,organophosphites such as triphenyl phosphite,tris-(2,6-dimethylphenyl)phosphite, tris-(mixed mono- anddi-nonylphenyl)phosphite or the like; phosphonates such asdimethylbenzene phosphonate or the like, phosphates such as trimethylphosphate, or the like, or combinations comprising at least one of theforegoing heat stabilizers. Heat stabilizers are generally used inamounts of about 0.01 to about 0.1 parts by weight, based on 100 partsby weight of polycarbonate copolymer and any additional polymer.

Light stabilizers and/or ultraviolet light (UV) absorbing additives canalso be used. Exemplary light stabilizer additives include, for example,benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole,2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole and 2-hydroxy-4-n-octoxybenzophenone, or the like, or combinations comprising at least one ofthe foregoing light stabilizers. Light stabilizers are generally used inamounts of about 0.01 to about 5 parts by weight, based on 100 parts byweight of polycarbonate copolymer and any additional polymer.

Exemplary UV absorbing additives include for example,hydroxybenzophenones; hydroxybenzotriazoles; hydroxybenzotriazines;cyanoacrylates; oxanilides; benzoxazinones;2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol (CYASORB®5411); 2-hydroxy-4-n-octyloxybenzophenone (CYASORB® 531);2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)-phenol(CYASORB® 1164); 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one)(CYASORB® UV-3638);1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane(UVINUL® 3030); 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one);1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane;nano-size inorganic materials such as titanium oxide, cerium oxide, andzinc oxide, all with a particle size less than or equal to about 100nanometers; or the like, or combinations comprising at least one of theforegoing UV absorbers. UV absorbers are generally used in amounts ofabout 0.01 to about 5 parts by weight, based on 100 parts by weight ofpolycarbonate copolymer and any additional polymer.

Plasticizers, lubricants, and/or mold release agents can also be used.There is considerable overlap among these types of materials, whichinclude, for example, phthalic acid esters such asdioctyl-4,5-epoxy-hexahydrophthalate;tris-(octoxycarbonylethyl)isocyanurate; tristearin; di- orpolyfunctional aromatic phosphates such as resorcinol tetraphenyldiphosphate (RDP), the bis(diphenyl)phosphate of hydroquinone and thebis(diphenyl)phosphate of bisphenol-A; poly-alpha-olefins; epoxidizedsoybean oil; silicones, including silicone oils; esters, for example,fatty acid esters such as alkyl stearyl esters, e.g. methyl stearate,stearyl stearate, pentaerythritol tetrastearate, and the like;combinations of methyl stearate and hydrophilic and hydrophobic nonionicsurfactants comprising polyethylene glycol polymers, polypropyleneglycol polymers, poly(ethylene glycol-co-propylene glycol) copolymers,or a combination comprising at least one of the foregoing glycolpolymers, e.g., methyl stearate and polyethylene-polypropylene glycolcopolymer in a suitable solvent; waxes such as beeswax, montan wax,paraffin wax, or the like. Such materials are generally used in amountsof about 0.1 to about 1 part by weight, based on 100 parts by weight ofpolycarbonate copolymer and any additional polymer.

The term “antistatic agent” refers to monomeric, oligomeric, orpolymeric materials that can be processed into polymer resins and/orsprayed onto materials or articles to improve conductive properties andoverall physical performance. Examples of monomeric antistatic agentsinclude glycerol monostearate, glycerol distearate, glyceroltristearate, ethoxylated amines, primary, secondary and tertiary amines,ethoxylated alcohols, alkyl sulfates, alkylarylsulfates,alkylphosphates, alkylaminesulfates, alkyl sulfonate salts such assodium stearyl sulfonate, sodium dodecylbenzenesulfonate or the like,quaternary ammonium salts, quaternary ammonium resins, imidazolinederivatives, sorbitan esters, ethanolamides, betaines, or the like, orcombinations comprising at least one of the foregoing monomericantistatic agents.

Exemplary polymeric antistatic agents include certain polyesteramidespolyether-polyamide (polyetheramide) block copolymers,polyetheresteramide block copolymers, polyetheresters, or polyurethanes,each containing polyalkylene glycol moieties polyalkylene oxide unitssuch as polyethylene glycol, polypropylene glycol, polytetramethyleneglycol, and the like. Such polymeric antistatic agents are commerciallyavailable, for example PELESTAT® 6321 antistatic (Sanyo) or PEBAX®MH1657 antistatic (Atofina), IRGASTAT® P18 and P22 antistatics(Ciba-Geigy). Other polymeric materials that can be used as antistaticagents are inherently conducting polymers such as polyaniline(commercially available as PANIPOL® EB polymer (from Panipol),polypyrrole and polythiophene (commercially available from Bayer), whichretain some of their intrinsic conductivity after melt processing atelevated temperatures. Specifically useful antistatic agents includetetraalkyl-onium salts of perfluoroalkane sulfonates, such as forexample the tetrabutylphosphonium salt of perfluorobutanesulfonate.These and others are described in U.S. Reexamined Pat. No. RE38530. Inone embodiment, carbon fibers, carbon nanofibers, carbon nanotubes,carbon black, or a combination comprising at least one of the foregoingcan be used in a polymeric resin containing chemical antistatic agentsto render the composition electrostatically dissipative. Antistaticagents are generally used in amounts of about 0.05 to about 0.5 parts byweight, based on 100 parts by weight of polycarbonate copolymer and anyadditional polymer.

Colorants such as pigment and/or dye additives can also be present.Useful pigments can include, for example, inorganic pigments such asmetal oxides and mixed metal oxides such as zinc oxide, titaniumdioxides, iron oxides, or the like; sulfides such as zinc sulfides, orthe like; aluminates; sodium sulfo-silicates sulfates, chromates, or thelike; carbon blacks; zinc ferrites; ultramarine blue; organic pigmentssuch as azos, di-azos, quinacridones, perylenes, naphthalenetetracarboxylic acids, flavanthrones, isoindolinones,tetrachloroisoindolinones, anthraquinones, enthrones, dioxazines,phthalocyanines, and azo lakes; Pigment Red 101, Pigment Red 122,Pigment Red 149, Pigment Red 177, Pigment Red 179, Pigment Red 202,Pigment Violet 29, Pigment Blue 15, Pigment Blue 60, Pigment Green 7,Pigment Yellow 119, Pigment Yellow 147, Pigment Yellow 150, and PigmentBrown 24; or combinations comprising at least one of the foregoingpigments. Pigments are generally used in amounts of about 0.0001 toabout 10 parts by weight, based on 100 parts by weight of polycarbonatecopolymer and any additional polymer.

Exemplary dyes are generally organic materials and include, for example,coumarin dyes such as coumarin 460 (blue), coumarin 6 (green), nile redor the like; lanthanide complexes; hydrocarbon and substitutedhydrocarbon dyes; polycyclic aromatic hydrocarbon dyes; scintillationdyes such as oxazole or oxadiazole dyes; aryl- or heteroaryl-substitutedpoly(C₂₋₈) olefin dyes; carbocyanine dyes; indanthrone dyes;phthalocyanine dyes; oxazine dyes; carbostyryl dyes;napthalenetetracarboxylic acid dyes; porphyrin dyes; bis(styryl)biphenyldyes; acridine dyes, anthraquinone dyes; cyanine dyes; methine dyes;arylmethane dyes; azo dyes; indigoid dyes, thioindigoid dyes, diazoniumdyes; nitro dyes; quinone imine dyes; aminoketone dyes; tetrazoliumdyes; thiazole dyes; perylene dyes, perinone dyes;bis-benzoxazolylthiophene (BBOT); triarylmethane dyes; xanthene dyes;thioxanthene dyes; naphthalimide dyes; lactone dyes; fluorophores suchas anti-stokes shift dyes which absorb in the near infrared wavelengthand emit in the visible wavelength, or the like; luminescent dyes suchas 7-amino-4-methylcoumarin;3-(2′-benzothiazolyl)-7-diethylaminocoumarin;2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole;2,5-bis-(4-biphenylyl)-oxazole; 2,2′-dimethyl-p-quaterphenyl;2,2-dimethyl-p-terphenyl; 3,5,3″″,5″″-tetra-t-butyl-p-quinquephenyl;2,5-diphenylfuran; 2,5-diphenyloxazole; 4,4′-diphenylstilbene;4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran;1,1′-diethyl-2,2′-carbocyanine iodide;3,3′-diethyl-4,4′,5,5′-dibenzothiatricarbocyanine iodide;7-dimethylamino-1-methyl-4-methoxy-8-azaquinolone-2;7-dimethylamino-4-methylquinolone-2;2-(4-(4-dimethylaminophenyl)-1,3-butadienyl)-3-ethylbenzothiazoliumperchlorate; 3-diethylamino-7-diethyliminophenoxazonium perchlorate;2-(1-naphthyl)-5-phenyloxazole; 2,2′-p-phenylen-bis(5-phenyloxazole);rhodamine 700; rhodamine 800; pyrene, chrysene, rubrene, coronene, orthe like; or combinations comprising at least one of the foregoing dyes.Dyes are generally used in amounts of about 0.0001 to about 5 parts byweight, based on 100 parts by weight of polycarbonate copolymer and anyadditional polymer.

Where a foam is desired, useful blowing agents include for example, lowboiling halohydrocarbons and those that generate carbon dioxide; blowingagents that are solid at room temperature and when heated totemperatures higher than their decomposition temperature, generate gasessuch as nitrogen, carbon dioxide, and ammonia gas, such asazodicarbonamide, metal salts of azodicarbonamide, 4,4′oxybis(benzenesulfonylhydrazide), sodium bicarbonate, ammoniumcarbonate, or the like, or combinations comprising at least one of theforegoing blowing agents. Blowing agents are generally used in amountsof about 1 to about 20 parts by weight, based on 100 parts by weight ofpolycarbonate copolymer and any additional polymer.

Useful flame retardants include organic compounds that includephosphorus, bromine, and/or chlorine. Non-brominated and non-chlorinatedphosphorus-containing flame retardants can be preferred in certainapplications for regulatory reasons, for example organic phosphates andorganic compounds containing phosphorus-nitrogen bonds.

One type of exemplary organic phosphate is an aromatic phosphate of theformula (GO)₃P═O, wherein each G is independently an alkyl, cycloalkyl,aryl, alkylaryl, or aralkyl group, provided that at least one G is anaromatic group. Two of the G groups can be joined together to provide acyclic group, for example, diphenyl pentaerythritol diphosphate.Exemplary aromatic phosphates include, phenyl bis(dodecyl)phosphate,phenyl bis(neopentyl)phosphate, phenylbis(3,5,5′-trimethylhexyl)phosphate, ethyl diphenyl phosphate,2-ethylhexyl di(p-tolyl)phosphate, bis(2-ethylhexyl)p-tolyl phosphate,tritolyl phosphate, bis(2-ethylhexyl)phenyl phosphate,tri(nonylphenyl)phosphate, bis(dodecyl)p-tolyl phosphate, dibutyl phenylphosphate, 2-chloroethyl diphenyl phosphate, p-tolylbis(2,5,5′-trimethylhexyl)phosphate, 2-ethylhexyl diphenyl phosphate, orthe like. A specific aromatic phosphate is one in which each G isaromatic, for example, triphenyl phosphate, tricresyl phosphate,isopropylated triphenyl phosphate, and the like.

Di- or polyfunctional aromatic phosphorus-containing compounds are alsouseful, for example, compounds of the formulas below:

wherein each G¹ is independently a hydrocarbon having 1 to about 30carbon atoms; each G² is independently a hydrocarbon or hydrocarbonoxyhaving 1 to about 30 carbon atoms; each X is independently a bromine orchlorine; m is 0 to 4, and n is 1 to about 30. Exemplary di- orpolyfunctional aromatic phosphorus-containing compounds includeresorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl)phosphate ofhydroquinone and the bis(diphenyl)phosphate of bisphenol A,respectively, their oligomeric and polymeric counterparts, and the like.

Exemplary flame retardant compounds containing phosphorus-nitrogen bondsinclude phosphonitrilic chloride, phosphorus ester amides, phosphoricacid amides, phosphonic acid amides, phosphinic acid amides,tris(aziridinyl)phosphine oxide. When present, phosphorus-containingflame retardants are generally present in amounts of about 0.1 to about30 parts by weight, more specifically about 1 to about 20 parts byweight, based on 100 parts by weight of polycarbonate copolymer and anyadditional polymer.

Halogenated materials can also be used as flame retardants, for examplehalogenated compounds and resins of formula (15):

wherein R is an alkylene, alkylidene or cycloaliphatic linkage, e.g.,methylene, ethylene, propylene, isopropylene, isopropylidene, butylene,isobutylene, amylene, cyclohexylene, cyclopentylidene, or the like; oran oxygen ether, carbonyl, amine, or a sulfur containing linkage, e.g.,sulfide, sulfoxide, sulfone, or the like. R can also consist of two ormore alkylene or alkylidene linkages connected by such groups asaromatic, amino, ether, carbonyl, sulfide, sulfoxide, sulfone, or thelike.

Ar and Ar′ in formula (15) are each independently mono- orpolycarbocyclic aromatic groups such as phenylene, biphenylene,terphenylene, naphthylene, or the like.

Y is an organic, inorganic, or organometallic radical, for example (1)halogen, e.g., chlorine, bromine, iodine, fluorine or (2) ether groupsof the general formula OB, wherein B is a monovalent hydrocarbon groupsimilar to X or (3) monovalent hydrocarbon groups of the typerepresented by R or (4) other substituents, e.g., nitro, cyano, and thelike, said substituents being essentially inert provided that there isgreater than or equal to one, specifically greater than or equal to two,halogen atoms per aryl nucleus.

When present, each X is independently a monovalent hydrocarbon group,for example an alkyl group such as methyl, ethyl, propyl, isopropyl,butyl, decyl, or the like; an aryl groups such as phenyl, naphthyl,biphenyl, xylyl, tolyl, or the like; and aralkyl group such as benzyl,ethylphenyl, or the like; a cycloaliphatic group such as cyclopentyl,cyclohexyl, or the like. The monovalent hydrocarbon group can itselfcontain inert substituents.

Each d is independently 1 to a maximum equivalent to the number ofreplaceable hydrogens substituted on the aromatic rings comprising Ar orAr′. Each e is independently 0 to a maximum equivalent to the number ofreplaceable hydrogens on R. Each a, b, and c is independently a wholenumber, including 0. When b is not 0, neither a nor c can be 0.Otherwise either a or c, but not both, can be 0. Where b is 0, thearomatic groups are joined by a direct carbon-carbon bond.

The hydroxyl and Y substituents on the aromatic groups, Ar and Ar′ canbe varied in the ortho, meta or para positions on the aromatic rings andthe groups can be in any possible geometric relationship with respect toone another.

Included within the scope of the above formula are bisphenols of whichthe following are representative: 2,2-bis-(3,5-dichlorophenyl)-propane;bis-(2-chlorophenyl)-methane; bis(2,6-dibromophenyl)-methane;1,1-bis-(4-iodophenyl)-ethane; 1,2-bis-(2,6-dichlorophenyl)-ethane;1,1-bis-(2-chloro-4-iodophenyl)ethane;1,1-bis-(2-chloro-4-methylphenyl)-ethane;1,1-bis-(3,5-dichlorophenyl)-ethane;2,2-bis-(3-phenyl-4-bromophenyl)-ethane;2,6-bis-(4,6-dichloronaphthyl)-propane;2,2-bis-(2,6-dichlorophenyl)-pentane;2,2-bis-(3,5-dibromophenyl)-hexane; bis-(4-chlorophenyl)-phenyl-methane;bis-(3,5-dichlorophenyl)-cyclohexylmethane;bis-(3-nitro-4-bromophenyl)-methane,bis-(4-hydroxy-2,6-dichloro-3-methoxyphenyl)-methane; and2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane 2,2bis-(3-bromo-4-hydroxyphenyl)-propane. Also included within the abovestructural formula are: 1,3-dichlorobenzene, 1,4-dibromobenzene,1,3-dichloro-4-hydroxybenzene, and biphenyls such as2,2′-dichlorobiphenyl, polybrominated 1,4-diphenoxybenzene,2,4′-dibromobiphenyl, and 2,4′-dichlorobiphenyl as well as decabromodiphenyl oxide, and the like.

Also useful are oligomeric and polymeric halogenated aromatic compounds,such as a copolycarbonate of bisphenol A and tetrabromobisphenol A and acarbonate precursor, e.g., phosgene. Metal synergists, e.g., antimonyoxide, can also be used with the flame retardant. When present, halogencontaining flame retardants are generally present in amounts of about 1to about 25 parts by weight, more specifically about 2 to about 20 partsby weight, based on 100 parts by weight of polycarbonate copolymer andany additional polymer.

Alternatively, the thermoplastic composition can be essentially free ofchlorine and bromine. Essentially free of chlorine and bromine as usedherein refers to materials produced without the intentional addition ofchlorine or bromine or chlorine or bromine containing materials. It isunderstood however that in facilities that process multiple products acertain amount of cross contamination can occur resulting in bromineand/or chlorine levels typically on the parts per million by weightscale. With this understanding it can be readily appreciated thatessentially free of bromine and chlorine can be defined as having abromine and/or chlorine content of less than or equal to about 100 partsper million by weight (ppm), less than or equal to about 75 ppm, or lessthan or equal to about 50 ppm. When this definition is applied to thefire retardant it is based on the total weight of the fire retardant.When this definition is applied to the thermoplastic composition it isbased on the total weight of the composition, excluding any filler.

Inorganic flame retardants can also be used, for example salts of C₁₋₁₆alkyl sulfonate salts such as potassium perfluorobutane sulfonate (Rimarsalt), potassium perfluoroctane sulfonate, tetraethylammoniumperfluorohexane sulfonate, and potassium diphenylsulfone sulfonate, andthe like; salts formed by reacting for example an alkali metal oralkaline earth metal (for example lithium, sodium, potassium, magnesium,calcium and barium salts) and an inorganic acid complex salt, forexample, an oxo-anion, such as alkali metal and alkaline-earth metalsalts of carbonic acid, such as Na₂CO₃, K₂CO₃, MgCO₃, CaCO₃, and BaCO₃or fluoro-anion complex such as Li₃AlF₆, BaSiF₆, KBF₄, K₃AlF₆, KAlF₄,K₂SiF₆, and/or Na₃AlF₆ or the like. When present, inorganic flameretardant salts are generally present in amounts of about 0.01 to about10 parts by weight, more specifically about 0.02 to about 1 parts byweight, based on 100 parts by weight of polycarbonate copolymer and anyadditional polymer.

Anti-drip agents can also be used in the composition, for example afibril forming or non-fibril forming fluoropolymer such aspolytetrafluoroethylene (PTFE). The anti-drip agent can be encapsulatedby a rigid copolymer as described above, for examplestyrene-acrylonitrile copolymer (SAN). PTFE encapsulated in SAN is knownas TSAN. Encapsulated fluoropolymers can be made by polymerizing theencapsulating polymer in the presence of the fluoropolymer, for examplean aqueous dispersion. TSAN can provide significant advantages overPTFE, in that TSAN can be more readily dispersed in the composition. Anexemplary TSAN can comprise about 50 wt % PTFE and about 50 wt % SAN,based on the total weight of the encapsulated fluoropolymer. The SAN cancomprise, for example, about 75 wt % styrene and about 25 wt %acrylonitrile based on the total weight of the copolymer. Alternatively,the fluoropolymer can be pre-blended in some manner with a secondpolymer, such as for, example, an aromatic polycarbonate resin or SAN toform an agglomerated material for use as an anti-drip agent. Eithermethod can be used to produce an encapsulated fluoropolymer. Antidripagents are generally used in amounts of 0.1 to 10 percent by weight,based on 100 percent by weight of polycarbonate copolymer and anyadditional polymer.

Radiation stabilizers can also be present, specifically gamma-radiationstabilizers. Exemplary gamma-radiation stabilizers include alkylenepolyols such as ethylene glycol, propylene glycol, 1,3-propanediol,1,2-butanediol, 1,4-butanediol, meso-2,3-butanediol, 1,2-pentanediol,2,3-pentanediol, 1,4-pentanediol, 1,4-hexandiol, and the like;cycloalkylene polyols such as 1,2-cyclopentanediol, 1,2-cyclohexanediol,and the like; branched alkylenepolyols such as2,3-dimethyl-2,3-butanediol (pinacol), and the like, as well asalkoxy-substituted cyclic or acyclic alkanes. Unsaturated alkenols arealso useful, examples of which include 4-methyl-4-penten-2-ol,3-methyl-pentene-3-ol, 2-methyl-4-penten-2-ol,2,4-di-methyl-4-pene-2-ol, and 9-decen-1-ol, as well as tertiaryalcohols that have at least one hydroxy substituted tertiary carbon, forexample 2-methyl-2,4-pentanediol (hexylene glycol), 2-phenyl-2-butanol,3-hydroxy-3-methyl-2-butanone, 2-phenyl-2-butanol, and the like, andcyclic tertiary alcohols such as 1-hydroxy-1-methyl-cyclohexane. Certainhydroxymethyl aromatic compounds that have hydroxy substitution on asaturated carbon attached to an unsaturated carbon in an aromatic ringcan also be used. The hydroxy-substituted saturated carbon can be amethylol group (—CH₂OH) or it can be a member of a more complexhydrocarbon group such as —CR⁴HOH or —CR₂ ⁴OH wherein R⁴ is a complex ora simple hydrocarbon. Specific hydroxy methyl aromatic compounds includebenzhydrol, 1,3-benzenedimethanol, benzyl alcohol, 4-benzyloxy benzylalcohol and benzyl benzyl alcohol. 2-Methyl-2,4-pentanediol,polyethylene glycol, and polypropylene glycol are often used forgamma-radiation stabilization. Gamma-radiation stabilizing compounds areused herein in amounts of 5 to 10 parts by weight based on 100 parts byweight of polycarbonate copolymer and any additional polymer.

The thermoplastic composition prepared from the polycarbonate copolymercan further be substantially transparent, having a low haze. Thus, a 3.2mm thick plaque molded from the thermoplastic composition desirably hasa haze of less than about 25%, specifically less than about 20%, morespecifically less than about 10%, and still more specifically less thanabout 5%, as measured using 3.2 mm thick plaques according toASTM-D1003-00. Similarly, a 3.2 mm thick plaque molded from thethermoplastic composition desirably has a % T of greater than or equalto about 70%, specifically greater than or equal to about 75%, morespecifically greater than or equal to about 80%, and still morespecifically greater than or equal to about 85%, according toASTM-D1003-00.

Thermoplastic compositions comprising the copolycarbonate can bemanufactured by various methods. For example, powdered copolycarbonate,other polymer (if present), and/or other optional components are firstblended, optionally with fillers in a HENSCHEL-Mixer® high speed mixer.Other low shear processes, including but not limited to hand mixing, canalso accomplish this blending. The blend is then fed into the throat ofa twin-screw extruder via a hopper. Alternatively, at least one of thecomponents can be incorporated into the composition by feeding directlyinto the extruder at the throat and/or downstream through a sidestuffer.Additives can also be compounded into a masterbatch with a desiredpolymeric resin and fed into the extruder. The extruder is generallyoperated at a temperature higher than that necessary to cause thecomposition to flow. The extrudate is immediately quenched in a waterbatch and pelletized. The pellets, so prepared, when cutting theextrudate can be one-fourth inch long or less as desired. Such pelletscan be used for subsequent molding, shaping, or forming.

Shaped, formed, or molded articles comprising the copolycarbonatecompositions are also provided. The polycarbonate compositions can bemolded into useful shaped articles by a variety of means such asinjection molding, extrusion, rotational molding, blow molding andthermoforming to form articles such as, for example, computer andbusiness machine housings such as housings for monitors, handheldelectronic device housings such as housings for cell phones, electricalconnectors, and components of lighting fixtures, ornaments, homeappliances, roofs, greenhouses, sun rooms, swimming pool enclosures, andthe like. In addition, the polycarbonate compositions can be used formedical applications, such as syringe barrels, sample containers,medicament containers, plastic vials, blood housings, filter housings,membrane housings, plungers, and the like.

In an embodiment, the polycarbonate composition can be cast from asuitable solvent to prepare supported membranes that can be used tofabricate filters or separators of blood products.

EXAMPLES

The copolycarbonates are further illustrated by the followingnon-limiting examples.

Molecular weight was determined using gel permeation chromatography, anda crosslinked styrene-divinylbenzene column operating at a flow rate of0.5-1.0 ml/min, a sample concentration of 1 mg/ml, and calibrated usingpolystyrene standards.

Surface contact angle measurements were performed using a Krüss DropShape Analysis System DSA10, depositing Milli-Q® purified water (aspurified using the purification system obtained from Millipore Corp.) asa fluid probe to form the sessile drop. Using the sessile drop method, adrop of water is automatically deposited on the surface or substrate tobe tested, and the contact angle (θ) between the surface and the 3 phasetangent line emanating from a point at the junction of the three phases,i.e., the surface, the water drop, and the air, is measured by thesystem automatically. In performing the measurement, the system depositsa 1.5 μl drop of water onto the specimen surface and measurements aretaken every 0.2 seconds for a period of 10 seconds by a CCD-camera. Fromthe live video image captured, the system automatically measures thecontact angle as the angle between the substrate and the tangent of thewater drop surface at the 3 phase contact line that the water drop makeswith the surface of the specimen, and the data are analyzed by DropShape Analysis software (DSA version 1.7, Krüss). The complete profileof the droplet was fitted by the tangent method to a general conicsection equation. The angles were determined both at the right and leftside. An average value is calculated for each drop and a total of fivedrops per sample are measured. The average of the five drops is taken asthe contact angle.

Glass transition temperature was determined by differential scanningcalorimetry using a Perkin Elmer Series 7 temperature ramp of 20°C./min. The samples were cycled through two successive temperature rampsand the glass transition temperature (Tg) was determined from the secondramp.

Haze (%) and transmittance (% T) was determined according to ASTMD1003-00 using a Gardner Haze Guard Dual, on 3.2 millimeter thick moldedplaques.

The relative platelet adhesion was determined by exposing injectionmolded parts in the form of microwell strips to a standardized amount ofplatelet rich plasma (PRP) obtained from a pooled blood source. Theexposure time was two hours at 37° C. The parts were then rinsed toremove non-adhering platelets, and the platelets remaining on thesurface were lysed with Triton® X-100 solution to release lactatedehydrogenase (LDH). The LDH released is a linear function of theplatelet count. The LDH concentration is determined with a commerciallyavailable LDH cytotoxicity kit that uses a calorimetric measurement(Cytotoxicity Detection Kit (LDH) available from Roche Applied Science;Catalog No. 11 644 793 001). All platelet adhesion values are reportedas a percentage of the value for a BPA polycarbonate standard that ismeasured concurrently with other test materials. Thus, a material whosereported value for platelet adhesion is 20% has ⅕ the number ofplatelets adhering to it as the BPA polycarbonate standard for theexposures used in the above protocol.

Copolycarbonates containing BPA and a PEG-PPG block copolymer providedas a PLURONIC® PEG-PPG copolymer (BASF) were made using atransesterification reaction of BPA and PLURONIC® PEG-PPG copolymer withbis(methyl-salicyl)carbonate according to the following general method.

Where a melt process was used, melt trans-esterification reactions werecarried out in a small or large-scale batch reactor and were runaccording to the following protocols. Residual sodium was cleaned fromthe glass reactor by soaking in 1 M HCl for at least 24 hours followedby rinsing at least 5 times with 18.2 milliohm deionized water. Thetemperature of the reactor was maintained using a heating mantle with atemperature controller and thermocouple. The pressure over the reactorwas controlled by a nitrogen bleed into a vacuum pump downstream of thedistillate collection flasks and measured with a pressure gauge.Catalyst solutions were prepared by diluting tetramethyl ammoniumhydroxide (TMAH) (Sachem, 25 wt % in water) and NaOH (Acros, 0.5 M) tothe proper concentrations with 18.2 milliohm water. All reactions wherecarried out with 2.5×10⁻⁵ mol of TMAH/total moles dihydroxy compounds,which was added in 100 microliter increments together with the NaOH. Inthe reaction, 1 eq. of NaOH was equal to 1.0×10⁻⁶ mol of NaOH/totalmoles dihydroxy compounds. Reactions were carried out in the presence of1 to 10 eq of NaOH. The total amount of added catalyst solution ismaintained at 100 microliter. Where higher levels of catalyst wereneeded, new solutions were prepared. The glass reactor tube was chargedwith the solid bisphenols (0.05879 to 0.05995 mol) and solidbis(methylsalicyl)carbonate (BMSC) (0.0605 mol), depending on thetargeted molar ratio of bisphenols to BMSC (1.03:1 to 1.01:1,respectively). The reactor was then assembled, sealed and the atmospherewas exchanged with nitrogen three times. The catalyst was added to themonomers. The reactor was brought to near atmospheric pressure andreaction time started at the same moment the heaters were set to thefirst set point.

The general reaction profile for a small (ca. 25 gram) scalemelt-process reaction is as follows. The reaction profile started withmelting the combined dihydroxy compounds, BMSC, and catalysts at 200° C.(170° C. if no high heat monomer is used), 1,000 millibars pressure andheating of the overhead to 100° C. After 6 minutes the stirrers wereswitched on (40 rpm). After 15 minutes, the pressure was reduced to 500millibars. After 45 minutes, the temperatures of the heaters were rampedup to 270° C. Then, at 50 minutes, the heaters were set to 300° C., andat the same time, the pressure was slowly reduced to achieve full vacuum(i.e., about 0.5 to 1 millibars). The time needed to reach full vacuumdepended on the behavior of the oligomer, typically approximately 4minutes. When 64 minutes of reaction time was reached the polymerizationwas stopped.

After completion of the polymerization, the reactor was brought back toatmospheric pressure with a gentle nitrogen flow. When atmosphericpressure was reached, stirring was stopped and the resulting materialdrained from the reactor tubes by opening a valve at the bottom of thereactor pushing out the material under a slight nitrogen over-pressure.The recovered material was then analyzed.

For melt experiments conducted with a non-activated carbonate, the samesetup and procedure was used as for the small scale but diphenylcarbonate was used instead of bis(methylsalicyl)carbonate (BMSC). Theglass reactor tube was charged with the solid monomers (0.087 mol) andsolid diphenyl carbonate (0.09 mol). The reaction profile started withmelting of the reactants at 180° C. and 1,000 millibars pressure, andthe overhead was heated to 100° C. After 6 minutes the stirrers wereswitched on (40 rpm). After 10 minutes, the temperature was increased to230° C. After 15 min, the pressure was reduced to 270 millibars. After70 minutes the pressure was reduced to 20 millibars. After 98 min, thetemperature was increased to 250° C. After 108 min, the pressure wasreduced to 0.5 to 1 millibars. For the experiment performed at 270° C.,after 115 min., the temperature was increased to 270° C. After 150 min,the reaction was stopped.

The general reaction profile for a large (ca. 8-10 kilogram) scalemelt-process reaction is as follows. A 50 liter stir tank was chargedwith BMSC (8.68 Kg, 26.3 moles), bisphenol-A (5.0 Kg, 21.9 moles),PPP-BP (1.51 Kg, 3.87 moles), PEG-PPG copolymer (e.g., PLURONIC® L61copolymer; 1.15 Kg, 0.606 moles), and p-cumyl phenol (0.11 Kg, 0.526moles) at room temperature. Two catalyst solutions were added:tetramethyl ammonium hydroxide (25 wt % aqueous solution, 0.50 ml), andsodium hydroxide (0.10M aqueous solution, 2.0 ml). The reactor wassealed, and purged with nitrogen three times to deoxygenate theatmosphere in the reactor. The mixture was then heated to 180° C. for atleast one hour. The resulting molten mixture was transferred by pumpinginto a 25 mm twin screw extruder at a rate of 8.0 Kg/hr. The extruderbarrel set temperatures were each 280° C. at a screw speed of 250-300rpm. The extruder was equipped with vacuum ports sufficient to effectefficient removal of methyl salicylate by-product. The high molecularweight polymer prepared in this way had residual methyl salicylatelevels of less than 500 ppm.

A series of polycarbonate copolymers were prepared to evaluate theinclusion of PEG-PPG copolymers into the polycarbonate backbone. Blockcopolymers of PEG and PPG commercialized by BASF under the tradenamePLURONIC® PEG-PPG copolymers were used. In these PEG-PPG copolymers, PEG(poly(ethylene glycol) is a hydrophilic block, and PPG (poly(propyleneglycol)) is the surface active component of the PEG-PPG copolymer. Twodifferent varieties of these PEG-PPG copolymers are available, asPLURONIC® (having a PEG-PPG-PEG) structure) and PLURONIC® R (having aPPG-PEG-PPG structure) PEG-PPG copolymers, as shown in (I) and (II)below, respectively. In (I) and (II), x, y, and z are each integers,which are be varied to provide the desired weight percentages of PEG andPEG and weight averaged molecular weight (Mw) in the PEG-PPG copolymersI and II as evaluated.

Table 1 shows the effect of the synthesis method on molecular weightbuildup for copolycarbonates, where use of activated carbonate is shownto provide higher Mw than use of non-activated carbonate.

TABLE 1 Weight % PLURONIC ® Synthesis Example 10R5 Method Mw (g/mol) Ex.1 15 Melt AC* 42,000 Ex. 2 (repeat 15 Melt 36,000 of Ex. 1) NAC* *ACusing activated carbonate, bis(methylsalicyl)carbonate; NAC using nonactivated carbonate (DPC)

A variety of copolycarbonates containing PLURONIC® PEG-PPG copolymerswere made using the transesterification process mentioned above, and thesamples were compression molded into bars at 190° C. for contact anglemeasurements (Table 2).

Table 2 shows the effect of PLURONIC® PEG-PPG copolymer concentration onthe contact angle. As a control, the copolycarbonate comparative exampleprepared using polyethylene glycol (CEx. 2) has the same wt % ofpolyethylene glycol as PLURONIC® 10R5 PEG-PPG copolymer (Ex. 3) andPLURONIC® L35 PEG-PPG copolymer (Ex. 4).

TABLE 2 Wt % Contact PEG-PPG copolymer Wt % in PEG in Angle ExampleCo-monomer Copolymer Copolymer (°) 3 PLURONIC ® 10R5 15 7.5 65 ± 3 4PLURONIC ® L35 15 7.5 60 ± 5 CEx. 2 Polyethylene Glycol 7.5 7.5 78 ± 2(Mw = 300 g/mole)

Table 2 shows that, for a constant amount of poly(ethylene glycol) in acopolycarbonate, the use of a PLURONIC® PEG-PPG copolymer produces amuch lower contact angle than the poly(ethylene glycol) containingcomparative example (CEx. 2). PLURONIC® PEG-PPG copolymers containpoly(propylene oxide) as the surface-active block, and as poly(propyleneoxide) is known to be more hydrophobic than polyethylene glycol. It isbelieved that the reduction in contact angle is achieved mostly throughthe poly(ethylene glycol). Therefore, a more hydrophilic surface isfound when a PLURONIC® PEG-PPG copolymer instead of poly(ethyleneglycol) is used as a co-monomer.

From the results obtained and as provided in Table 2, it was determinedthat the decrease in contact angle by addition of hydrophilic monomer tothe composition is not obvious. Without wishing to be bound by theory,it can be concluded that for copolycarbonates prepared using a PEG-PPGdiblock copolymer, the presence of a surface active group component(PPG) appears to bring the hydrophilic (PEG) groups to the polymersurface, providing the PEG blocks with surface access and therebydecreasing the surface contact angle. In addition, the use of a blockcopolymer of the hydrophilic component (PEG) and the surface-activecomponent (PPG) works better than the random incorporation of bothcomponents into the polymer chain.

Table 3 shows the static water contact angle, Tg, and platelet adhesionresults for additional examples of polycarbonate copolymers made withPEG and PEG-PPG block copolymers. The contact angle and Tg results wereobtained using molded plaques, whereas the platelet adhesion resultswere obtained from molded polymer samples as described above.

TABLE 3 % wt Static glycol Water Platelet monomer Contact AdhesionExample Composition (mol %) in polymer Angle (°) Tg (° C.) (% v. BPA-PC)CEx. 3 100% BPA 0 83 152 100 CEx. 4 70% BPA, 30% PPPBP 0 86 200 79 CEx.5 57.7% BPA, 31.4% PPPBP, 14 81 121 53 10.9% PEG400^(b) CEx. 6 63.2%BPA, 34.3% PPPBP, 14 66 125 33 2.5% PEG2000^(b) CEx. 7 74% BPA, 21.5%PPPBP, 9 72 138 32 2.7% PPG1000^(b) CEx. 8 59.8% BPA, 32.5% PPPBP, 13 70133 19 3.7% PEG600, 2.2% PPG1000^(b) Ex. 5 97.7% BPA, 2.3% 15 63 97 —PLURONIC ® L35^(a) Ex. 6 62.0% BPA, 33.3% PPPBP, 14 65 126 5 2.5%PLURONIC ® L35^(a) Ex. 7 63.2% BPA, 34.3% PPPBP, 14 67 127 4 2.5%PLURONIC ® L61^(a) Ex. 8 81.5% BPA, 14.4% PPPBP, 14 66 110 5 2.1%PLURONIC ® L61^(a) Ex. 9 71.8% BPA, 23.9% PPPBP, 23 67 84 3 4.3%PLURONIC ® L61^(a) ^(a)PLURONIC ® L35 and L61 are PEG-PPG blockcopolymers from BASF Corporation having the structure PEG-PPG-PEG.^(b)PEG400, PEG600, and PEG2000 are polyethylene glycols with nominalmolecular weights of 400, 600, and 2000, respectively. PPG1000 is apolypropylene glycol with a nominal molecular weight of 1000.

In Table 3, it can be seen that there is a distinct difference insurface contact angle between copolycarbonates prepared using singleblocks of PEG (CEx. 5, 6, and 8) or PPG (CEx. 7) and copolycarbonatesprepared using PEG-PPG block copolymers (Ex. 5-9). PLURONIC® L61 inparticular provides low contact angle even where the amount of the BPAcomponent is high relative to PPPBP (Ex. 8), even when compared to asimilar molar amount of PLURONIC® L35 with higher PPPBP (Ex. 6);however, the Tg for Ex. 8 is also reduced versus Ex. 6, a function ofthe higher PPPBP loading in the latter polymer.

In addition, there is a dramatic decrease seen in platelet adhesionversus bisphenol A polycarbonate for the copolycarbonates prepared usingPLURONIC® PEG-PPG copolymers (Exs. 6-9), as compared to thecopolycarbonates prepared using no hydrophilic or hydrophobic blocks(PEG, PPG, or a combination; CExs. 3-8). The platelet adhesion valuesfor the examples are all in the single digits, well below that of thecomparative examples.

Increasing the amount of PLURONIC® PEG-PPG copolymer in the compositionprovided a decrease in contact angle. Table 4 shows the effect of staticwater contact angle for different loadings of PLURONIC® 10R5copolymerized with BPA and PPPBP in different molar ratios. (PLURONIC®10R5 is a PEG-PPG block copolymer from BASF Corporation having thestructure PPG-PEG-PPG). In addition, FIG. 1 shows a plot of loading ofPLURONIC® 10R5 versus static water contact angle.

TABLE 4 Static Water PPPBP PLURONIC ® Contact Angle Example BPA (mol%)^(c) (mol %)^(c) 10R5 (wt %) (°) Ex. 10 55 45 20 61 Ex. 11 65 35 15 60Ex. 12 73 27 10 68 Ex. 13 83 17 5 70 CEx. 9 65 35 0 78 ^(c)Molepercentages of BPA and PPPBP are based on the combined no. of moles ofBPA and PPPBP.

As seen in the data in Table 4, and in FIG. 1, the water contact angleincreases with increasing amounts of BPA and PLURONIC® 10R5 (anddecreasing levels of PPPBP). The static water contact angle reaches aplateau at values of 68 to 70° at PLURONIC® 10R5 component levels of 5to 10 wt %, and BPA levels (relative to BPA+PPPBP in thecopolycarbonates) of 73 to 83 mol % (Exs. 12 and 13). At a compositionof 20 wt % hydrophilic monomer, the contact angle reaches a minimumlevel (Ex. 10).

By increasing the molecular weight of PPG in the PLURONIC® polymer, hazeincreases and % transmission decreases. In the studied range, theseproperties show no correlation with the Mw of PEG in the PLURONIC®polymer. Table 5 shows the percent haze and transmission ofPEG-PPG/BPA/PPPBP terpolymer plaques versus molecular weight of PPG inthe PEG-PPG block copolymer. All compositions presented in the tablehave 35 mol % PPPBP and 65 mol % BPA. The data are plotted as molecularweight of PPG versus haze in FIG. 2, and versus % T in FIG. 3.

TABLE 5 Hydrophilic Hydrophilic monomer Mw PPG Mw PEG TransmissionExample monomer (wt %) (g/mol) (g/mol) Haze (%) (%) Ex. 14 PLURONIC ®L35 13 950 950 1.93 78.2 Ex. 15 PLURONIC ® L35 14 950 950 1.92 76.3 CEx.10 PLURONIC ® P85 15 2300 2300 43.5 70.7 Ex. 16 PLURONIC ® L61 15 1800200 2.16 83.9 CEx. 11 PLURONIC ® 31R1 15 2925 325 102 18.1 Ex. 17PLURONIC ® 17R2 15 1720 430 2.78 83.2 CEx. 12 PLURONIC ® 25R2 15 2480620 93.7 28.5 Ex. 18 PLURONIC ® 10R5 15 1000 960 1.86 82.8

As seen in Table 5, copolymers prepared using PLURONIC® L35 (Exs. 14 and15), PLURONIC® L61 (Ex. 16), PLURONIC® 17 (Ex. 17), and PLURONIC® 10R5(Ex. 18) PEG-PPG copolymers provided acceptable values for both haze andtransmission. The length of the PPG chain appears to affect opticalproperties, as shown in FIGS. 2 and 3. At an Mw of 1,800 g/mol or lessfor the PPG block (Ex. 16), no increase in haze (See FIG. 2) orreduction in % T (See FIG. 3) is apparent.

Table 6 shows the effect of different “high heat” monomers on the Tg ofcopolycarbonates prepared using a high heat monomer, BPA, and PLURONIC®L35. The particular high heat (“HH”) monomers evaluated include PPPBP,TCDBP, BPI, and phenolphthalein (abbreviated “PPN” in Table 6). Theresults are as shown below.

TABLE 6 mol % % mol PLURONIC ® L35 % wt glycol HH % mol HH PEG-PPGmonomer Tg Mw Example monomer BPA monomer copolymer in polymer (° C.)(g/mol) Ex. 19 none 97.9 0.0 2.1 15.2 79 42027 CEx. 13 PPPBP 65 35 0 0196 29802 Ex. 20 PPPBP 63.6 33.7 2.7 15.4 122 40748 CEx. 14 PPN 65.534.5 0.0 0 195 56541 Ex. 21 PPN 63.5 33.6 2.9 18.0 106 94624 CEx. 15TCDBP 65.1 34.9 0.0 0 193 42027 Ex. 22 TCDBP 63.6 33.5 2.9 17.9 108 N/ACEx. 16 BPI 64.9 35.1 0 0 165 68268 Ex. 23 BPI 62.8 34.2 3.1 22.0 8730298 ^(c)Mole percentages of BPA and HH monomer are based on thecombined no. of moles of BPA and PPPBP.

As seen in Table 6, increases in Tg were observed versus theBPA-PLURONIC® L35 copolymer for all high heat monomers used. The lowestTg (87° C.) was observed for BPI, which also had a slightly higherPEG-PPG copolymer loading (3.1 mol % versus 2.7 mol % for Ex. 20 and 2.9mol % for Exs. 21 and 22). The highest Tg (122° C.) and hence thegreatest increase per unit HH monomer loading was observed for PPPBP.

The singular forms “a,” “an,” and “the” include plural referents unlessthe context clearly dictates otherwise. Unless defined otherwise,technical and scientific terms used herein have the same meaning as iscommonly understood by one of skill in the art to which this inventionbelongs. The endpoints of all ranges directed to the same component orproperty are inclusive and independently combinable. The suffix “(s)” asused herein is intended to include both the singular and the plural ofthe term that it modifies, thereby including at least one of that term(e.g., the colorant(s) includes at least one colorants). “Optional” or“optionally” means that the subsequently described event or circumstancecan or can not occur, and that the description includes instances wherethe event occurs and instances where it does not. All references areincorporated herein by reference.

Compounds are described using standard nomenclature. For example, anyposition not substituted by any indicated group is understood to haveits valency filled by a bond as indicated, or a hydrogen atom. A dash(“-”) that is not between two letters or symbols is used to indicate apoint of attachment for a substituent. For example —CHO is attachedthrough carbon of the carbonyl group. The term “substituted” as usedherein means that any at least one hydrogen on the designated atom orgroup is replaced with another group, provided that the designatedatom's normal valence is not exceeded. When the substituent is oxo(i.e., ═O), then two hydrogens on the atom are replaced. Also as usedherein, the term “combination” is inclusive of blends, mixtures, alloys,reaction products, and the like.

As used herein, the term “hydrocarbyl” refers broadly to a substituentcomprising carbon and hydrogen, optional with at least one heteroatoms,for example, oxygen, nitrogen, halogen, or sulfur; the term “alkyl”refers to a straight or branched chain monovalent hydrocarbon group;“alkylene” refers to a straight or branched chain divalent hydrocarbongroup; “alkylidene” refers to a straight or branched chain divalenthydrocarbon group, with both valences on a single common carbon atom;“cycloalkyl” refers to a non-aromatic monovalent monocyclic ormulticyclic hydrocarbon group having at least three carbon atoms;“cycloalkylene” refers to a non-aromatic divalent monocyclic ormulticyclic hydrocarbon group having at least three carbon atoms; “aryl”refers to an aromatic monovalent group containing only carbon in thearomatic ring or rings; “arylene” refers to an aromatic divalent groupcontaining only carbon in the aromatic ring or rings; “alkylaryl” refersto an aryl group that has been substituted with an alkyl group asdefined above, with 4-methylphenyl being an exemplary alkylaryl group;“arylalkyl” refers to an alkyl group that has been substituted with anaryl group as defined above, with benzyl being an exemplary arylalkylgroup; “acyl” refers to a an alkyl group as defined above with theindicated number of carbon atoms attached through a carbonyl carbonbridge (—C(═O)—); “alkoxy” refers to an alkyl group as defined abovewith the indicated number of carbon atoms attached through an oxygenbridge (—O—); and “aryloxy” refers to an aryl group as defined abovewith the indicated number of carbon atoms attached through an oxygenbridge (—O—).

An “organic group” as used herein means a saturated or unsaturated(including aromatic) hydrocarbon having a total of the indicated numberof carbon atoms and that can be unsubstituted or unsubstituted with oneor more of halogen, nitrogen, sulfur, or oxygen, provided that suchsubstituents do not significantly adversely affect the desiredproperties of the composition; for example transparency; heatresistance, or the like. Exemplary substituents include alkyl alkenyl,alkynyl, cycloalkyl, aryl, alkylaryl, arylalkyl, —NO₂, SH, —CN, OH,halogen, alkoxy, aryloxy, acyl, alkoxy carbonyl, and amide groups.

While typical embodiments have been set forth for the purpose ofillustration, the foregoing descriptions should not be deemed to be alimitation on the scope herein. Accordingly, various modifications,adaptations, and alternatives can occur to one skilled in the artwithout departing from the spirit and scope herein.

1. A polycarbonate copolymer comprising, A) 5 to 30 weight percent of astructure derived from a dihydroxy alkylene oxide compound selected fromthe group consisting of formula (1a) and formula (1b):H-(E-X)_(l)—OH  (1a)H-(E-X-E)_(l)-OH  (1b) wherein E and X are different and each andindependently are selected from the group consisting of formula (2a) andformula (2b):—(OCH₂CH₂)_(m)—  (2a)—(OCHRCH₂)_(n)—  (2b) wherein R is a C₁₋₈ alkyl group; l, m, and n areintegers greater than or equal to 1; and wherein the weight averagemolecular weight of the total amount of the structures corresponding toformula (2b) in the copolymer is between 100 and 2,000 g/mol; and B) 70to 95 weight percent of a structure derived from a dihydroxy aromaticcompound, wherein the weight percentages are based on the total weightof the structures of A) and B).
 2. The polycarbonate copolymer of claim1 wherein the dihydroxy aromatic compound comprises a bisphenol offormula (4):

wherein R^(a) and R^(b) each independently represent halogen or C₁₋₁₂alkyl; p and q are each independently integers of 0 to 4, and X^(a) is—O—, —S—, —S(O)—, S(O)₂—, or one of the groups of formula (5):

wherein R^(c) and R^(d) are each independently hydrogen, C₁₋₁₂ alkyl,cyclic C₁₋₁₂ alkyl, C₇₋₁₂ arylalkyl, C₁₋₁₂ heteroalkyl, or cyclic C₇₋₁₂heteroarylalkyl, and R^(e) is a divalent C₁₋₁₂ hydrocarbon group.
 3. Thepolycarbonate copolymer of claim 2 wherein R^(c) and R^(d) are methyl,and p and q are
 0. 4. The polycarbonate copolymer of claim 1 wherein Ris methyl.
 5. The polycarbonate copolymer of claim 1 wherein l is 1; Ecorresponds to formula (2a), and X corresponds to formula (2b); m is 2to 55; and n is 2 to
 40. 6. The polycarbonate copolymer of claim 1wherein l is 1; X corresponds to formula (2a) and E corresponds toformula (2b); m is 3 to 120; and n is 2 to
 30. 7. The polycarbonatecopolymer of claim 1, where the dihydroxy aromatic compound B) comprisesa combination of two or more dihydroxy aromatic compounds that are notidentical.
 8. The polycarbonate copolymer of claim 1 wherein an articlewith a thickness of 3.2 mm and molded from the polycarbonate copolymerhas a haze of less than or equal to 5% according to ASTM D1003-00. 9.The polycarbonate copolymer of claim 1 wherein an article with athickness of 3.2 mm and molded from the polycarbonate copolymer has apercent transmittance of greater than or equal to 70% according to ASTMD1003-00.
 10. The polycarbonate copolymer of claim 1 wherein the surfacecontact angle of an article molded from the thermoplastic polycarbonateis less than or equal to 70 degrees.
 11. The polycarbonate copolymer ofclaim 1, wherein an article molded from the polycarbonate copolymer hasa % platelet adhesion that is less than that of a comparative articlemolded from bisphenol A polycarbonate.
 12. The polycarbonate copolymerof claim 1, wherein the polycarbonate comprises structural units derivedfrom an active carbonate.
 13. A polycarbonate copolymer comprising, A) 5to 30 weight percent of a structure derived from a dihydroxy alkyleneoxide compound selected from the group consisting of formula (1a) andformula (1b):H-(E-X)_(l)—OH  (1a)H-(E-X-E)_(l)-OH  (1b) wherein E and X are different and each andindependently are selected from the group consisting of formula (2a) andformula (2b):—(OCH₂CH₂)_(m)—  (2a)—(OCHRCH₂)_(n)—  (2b) wherein R is a C₁₋₈ alkyl group; l, m, and n areintegers greater than or equal to 1; and wherein the weight averagemolecular weight of the total amount of the structures corresponding toformula (2b) in the copolymer is between 100 and 2,000 g/mol; and B) 70to 95 weight percent of a structure derived from a dihydroxy aromaticcompound, wherein the weight percentages are based on the total weightof the structures of A) and B), and wherein the polycarbonate comprisesstructural units derived from an activated aromatic carbonate.
 14. Thecomposition according to claim 13, wherein the activated aromaticcarbonate is bis(methylsalicyl)carbonate.
 15. The composition accordingto claim 13, wherein the structural units derived from the activatedaromatic carbonate are end groups.
 16. A thermoplastic compositioncomprising the polycarbonate copolymer of claim 1 and an additive. 17.The thermoplastic composition of claim 16 wherein the additive comprisesan impact modifier, a filler, an ionizing radiation stabilizer, anantioxidant, a heat stabilizer, a light stabilizer, an ultraviolet lightabsorber, a plasticizer, a lubricant, a mold release agent, anantistatic agent, a pigment, a dye, a flame retardant, an anti-dripagent, or a combination comprising at least one of the foregoingadditives.
 18. A thermoplastic polycarbonate copolymer consistingessentially of: A) 5 to 30 weight percent of a structure derived from adihydroxy alkylene oxide compound selected from the group consisting offormula (1a) and formula (1b):H-(E-X)_(l)—OH  (1a)H-(E-X-E)_(l)-OH  (1b) wherein E and X are different and each andindependently are selected from the group consisting of formula (2a) andformula (2b):—(OCH₂CH₂)_(m)—  (2a)—(OCHRCH₂)_(n)—  (2b) wherein R is a C₁-C₈ alkyl group; l, m, and n areintegers greater than or equal to 1; and wherein the weight averagemolecular weight of the total amount of the structures corresponding toformula (2b) in the copolymer is between 100 and 2,000 g/mol; and B) 70to 95 weight percent of a structure derived from a dihydroxy aromaticcompound, wherein the weight percentages are based on the total weightof the structures of A) and B).
 19. A method of preparing apolycarbonate copolymer comprising copolymerizing: A) 5 to 30 weightpercent of a dihydroxy alkylene oxide compound selected from the groupconsisting of formula (1a) and formula (1b):H-(E-X)_(l)—OH  (1a)H-(E-X-E)_(l)-OH  (1b) wherein E and X are different and each andindependently are selected from the group consisting of formula (2a) andformula (2b):—(OCH₂CH₂)_(m)—  (2a)—(OCHRCH₂)_(n)—  (2b) wherein R is a C₁₋₈ alkyl group; l, m, and n areintegers greater than or equal to 1; and wherein the weight averagemolecular weight of the total amount of the structures corresponding toformula (2b) in the copolymer is between 100 and 2,000 g/mol; and B) 70to 95 weight percent of a dihydroxy aromatic compound, wherein theweight percentages are based on the total weight of the structures of A)and B); and a carbonylating agent.
 20. The method of claim 19, whereinthe copolymerizing is done by an interfacial polymerization method, andthe carbonylating agent is phosgene.
 21. The method of claim 19, whereinthe copolymerizing is done by a melt-polymerization method, thecarbonylating agent is an aryl carbonate.
 22. The method of claim 19wherein a thermal stabilizer is included during copolymerizing.
 23. Themethod of claim 21, wherein the aryl carbonate is phenyl carbonate orbis(methyl salicyl)carbonate.
 24. A method comprising reacting together,in the presence of a catalyst: A) 5 to 30 weight percent or a dihydroxyalkylene oxide compound selected from the group consisting of formula(1a) and formula (1b):H-(E-X)_(l)—OH  (1a)H-(E-X-E)_(l)-OH  (1b) wherein E and X are different and each andindependently are selected from the group consisting of formula (2a) andformula (2b):—(OCH₂CH₂)_(m)—  (2a)—(OCHRCH₂)_(n)—  (2b) wherein R is a C₁₋₈ alkyl group; l, m, and n areintegers greater than or equal to 1; and wherein the weight averagemolecular weight of the total amount of the structures corresponding toformula (2b) in the copolymer is between 100 and 2,000 g/mol; and B) 70to 95 weight percent of a dihydroxy aromatic compound, wherein theweight percentages are based on the total weight of the structures of A)and B); and one or more activated diaryl carbonate of the formula (12):

wherein Ar is a substituted C₆₋₃₀ aromatic group.
 25. The methodaccording to claim 24, wherein the catalyst comprises: a.) an alphacatalyst selected from the group consisting of alkali metal salts andalkaline earth metal salt; and b.) a beta catalyst selected from thegroup consisting of a quaternary ammonium compound and a quaternaryphosphonium compound.
 26. The method according to claim 24, wherein theactivated aromatic carbonate has formula (13):

wherein Q¹ and Q² are each independently an activating group present onA¹ and A² respectively, positioned ortho to the carbonate linkage; A¹and A² are each independently aromatic rings which can be the same ordifferent; “d” and “e” have a value of 0 to a maximum equivalent to thenumber of replaceable hydrogen groups substituted on the aromatic ringsA¹ and A² respectively, and the sum “d+e” is greater than or equal to 1;R¹ and R² are each independently a C₁₋₃₀ aliphatic group, a C₃₋₃₀cycloaliphatic group, a C_(5,-30) aromatic group, cyano, nitro orhalogen; “b” has a value of 0 to a maximum equivalent to the number ofreplaceable hydrogen atoms on the aromatic ring A¹ minus “d”; and “c” isa whole number from 0 to a maximum equivalent to the number ofreplaceable hydrogen atoms on the aromatic ring A² minus e.
 27. Themethod according to claim 26, wherein the activated aromatic carbonateis bis(methylsalicyl)carbonate.
 28. An article comprising thepolycarbonate copolymer of claim 1.